CN107312110B - A kind of N- thiosemicarbazides-O- quaternary ammonium salt chitosan oligosaccharide and preparation method and application - Google Patents
A kind of N- thiosemicarbazides-O- quaternary ammonium salt chitosan oligosaccharide and preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of N- thiosemicarbazides-O- quaternary ammonium salt chitosan oligosaccharide and preparation method and application.Its structural formula are as follows:Preparation method is react with the amino on chitosan oligosaccharide using formaldehyde obtaining N- methylene chitosan oligosaccharide, then using C in 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride and the N- methylene chitosan oligosaccharide6Hydroxyl on position carries out reaction and obtains N- methylene-O- quaternary ammonium salt chitosan oligosaccharide, finally carries out addition reaction using the carbon-to-nitrogen double bon of thiosemicarbazides and the N- methylene-O- quaternary ammonium salt chitosan oligosaccharide and obtains N- thiosemicarbazides-O- quaternary ammonium salt chitosan oligosaccharide.It is poor, easy to be dissolved the problem of corroding and usable in acid, neutral, alkaline aqueous solution that the present invention not only solves chitosan oligosaccharide, chitosan derivatives adsorptivity.Meanwhile its bacteriostasis property is improved, there is good effect in the absorption of metal ion and inhibition bacterium.
Description
Technical field
The present invention relates to a kind of N- thiosemicarbazides-O- quaternary ammonium salt chitosan oligosaccharide and preparation method and application.
Background technique
The sharply development of modern industry, causes water resource pollution to get worse, or even has fed through to the safety of underground water and asked
Topic.Equally, a large amount of existing corrosion phenomenons and microbial contamination seriously affect industrial plants, public health infrastructure and daily set
Apply using safe.The use of some materials such as metal corrosion inhibitor, metal ion adsorbent and bacteriostatic agent, depends on mostly
Chemical synthetic material.Bring pollution, materials'use process band during the inefficient of traditional material, highly energy-consuming and chemical synthesis
The new pollution come, so that developing and using the water treatment agent, preservative and fungicide gesture of environmentally protective natural source product must
Row.The use that pure chemistry synthetic agent and material can be reduced also corresponds to the thinking of sustainable development.
Chitosan oligosaccharide is the post-rift degradation product of chitosan main chain, also referred to as chitin oligo saccharide, scientific name oligosaccharides gucosamine.It is that shell is poly-
Good water solubility, the low molecular weight that function is big, bioactivity is high, the degree of polymerization is made of sugar is degraded through physics, chemistry or enzyme
Chitosan.Chitosan oligosaccharide is the unique basic amine group oligosaccharides containing positive charge in nature, green natural, without side-effects, thus energy
Enough it is used as a new class of physiological activator.
Chinese patent CN201510539571.7 discloses a kind of system of thiocarbamide acetic acid grafted chitosan heavy metal absorbent
Preparation Method, it is modified by thiocarbamide acetic acid grafted chitosan, although its absorption stability is made to increase, this kind of sulphur
Allanic acid grafted chitosan lacks effective hydrophilic radical, and flocculating effect in water is poor, therefore adsorptivity is undesirable, this makes
It is in the application by many limitations.
Summary of the invention
It is the performance on bactericidal property in absorption to the modification of chitosan oligosaccharide from the prior art, present inventor has found that it is deposited
In following problems: chitosan oligosaccharide absorption property is poor, is easily dissolved corrosion, can not use for a long time in acid or alkaline aqueous solution.
In order to solve the deficiencies in the prior art, an object of the present invention is to provide a kind of N- thiosemicarbazides-O- quaternary ammonium salt
Chitosan oligosaccharide, structural formula are as follows:
It is by chitosan oligosaccharide through amino and C6The hydroxyl of position is obtained by modified, wherein the number-average molecular weight of the chitosan oligosaccharide
It is 200~3000.
The second object of the present invention is to provide a kind of preparation method of N- thiosemicarbazides-O- quaternary ammonium salt chitosan oligosaccharide, using first
Aldehyde, which react with the amino on chitosan oligosaccharide, obtains N- methylene chitosan oligosaccharide, then uses the chloro- 2- Hydroxyproyl Trimethyl chlorination of 3-
C in ammonium and the N- methylene chitosan oligosaccharide6Hydroxyl on position carries out reaction and obtains N- methylene-O- quaternary ammonium salt chitosan oligosaccharide, finally
Addition reaction is carried out using the carbon-to-nitrogen double bon of thiosemicarbazides and the N- methylene-O- quaternary ammonium salt chitosan oligosaccharide and obtains N- amino sulphur
Urea-O- quaternary ammonium salt chitosan oligosaccharide.
The present invention first reacts the amino on chitosan oligosaccharide to using formaldehyde, and amino is made to be changed into N- methylene, prevents
Only the hydroxyl on chitosan oligosaccharide on the position C6 carries out quaternised modified while carrying out quaternization reaction to amino, moreover it is possible to convert amino
At other groups, facilitates and carry out other combination reactions.Secondly, the present invention is anti-using thiosemicarbazides and carbon-to-nitrogen double bon progress addition
It answers, reaction efficiency is high, and other impurities are not generated in reaction process, without being separated.The N- thiosemicarbazides-of this method preparation
The problem of O- quaternary ammonium salt chitosan oligosaccharide, it is poor to not only solve chitosan oligosaccharide, chitosan derivatives adsorptivity, is easily dissolved corrosion, and
It can be used in acid, neutral, alkaline aqueous solution.Meanwhile its bacteriostasis property is improved, in the absorption and inhibition of metal ion
There is good effect on bacterium.
The third object of the present invention is to provide a kind of above-mentioned N- thiosemicarbazides-O- quaternary ammonium salt chitosan oligosaccharide or above method preparation
N- thiosemicarbazides-O- quaternary ammonium salt chitosan oligosaccharide inhibiting the application in bacterium or adsorption of metal ions.
The fourth object of the present invention is to provide a kind of above-mentioned N- thiosemicarbazides-O- quaternary ammonium salt chitosan oligosaccharide or above method preparation
The application in the treatment of waste water of N- thiosemicarbazides-O- quaternary ammonium salt chitosan oligosaccharide.
The invention has the benefit that
(1) N- thiosemicarbazides-O- quaternary ammonium salt chitosan oligosaccharide prepared by the present invention solves chitosan oligosaccharide, chitosan derivatives are inhaled
The problem of attached property is poor, is easily dissolved corrosion, there is good effect in the absorption of metal ion.
(2) N- thiosemicarbazides-O- quaternary ammonium salt chitosan oligosaccharide prepared by the present invention, due on side chain instead of quaternary ammonium salt group,
Substantially increase its biocidal property, can be used as fungicide come using.
(3) N- thiosemicarbazides-O- quaternary ammonium salt chitosan oligosaccharide prepared by the present invention solves chitosan derivatives only in acyclic acidic
It is dissolved under border using limited problem, there is good metal adsorption complexing power and bacteriostasis, be used as bacteriostatic agent
With metal chelating agent applied to antibacterial and heavy metal contaminants process field.
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singular
Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
Heretofore described organic solvent is organic matter that can be miscible with water, such as methanol, ethyl alcohol, propyl alcohol, isopropyl
Alcohol, acetone etc..
Heretofore described alkali is the compound that pH value after being dissolved in water is greater than 7, for example, sodium hydroxide, potassium hydroxide,
Sodium carbonate etc..
As background technique is introduced, exist in the prior art chitosan oligosaccharide absorption property is poor, easily dissolved burn into can not
The deficiency used in acid or alkaline aqueous solution, in order to solve technical problem as above, present applicant proposes a kind of N- amino
Thiocarbamide-O- quaternary ammonium salt chitosan oligosaccharide.
A kind of exemplary embodiment of the application provides a kind of N- thiosemicarbazides-O- quaternary ammonium salt chitosan oligosaccharide, structural formula
It is as follows:
It is by chitosan oligosaccharide through amino and C6The hydroxyl of position is obtained by modified, wherein the number-average molecular weight of the chitosan oligosaccharide
It is 200~3000.
Another exemplary embodiment of the application provides a kind of preparation of N- thiosemicarbazides-O- quaternary ammonium salt chitosan oligosaccharide
Method react with the amino on chitosan oligosaccharide obtaining N- methylene chitosan oligosaccharide, then uses the chloro- 2- hydroxypropyl of 3- using formaldehyde
C in trimethyl ammonium chloride and the N- methylene chitosan oligosaccharide6Hydroxyl on position carries out reaction and obtains N- methylene-O- quaternary ammonium salt crust
Oligosaccharides finally carries out addition reaction acquisition using the carbon-to-nitrogen double bon of thiosemicarbazides and the N- methylene-O- quaternary ammonium salt chitosan oligosaccharide
N- thiosemicarbazides-O- quaternary ammonium salt chitosan oligosaccharide.
The present invention prepares N- thiosemicarbazides-O- quaternary ammonium salt chitosan oligosaccharide, and the substitution on hydroxyl is predominantly located at C6On position, C3
Degree of substitution on position only accounts for the 5% of the total degree of substitution of hydroxyl, therefore C is only considered in explanation below6The substitution of position hydroxyl.
The present invention first reacts the amino on chitosan oligosaccharide to using formaldehyde, and amino is made to be changed into N- methylene, prevents
The only C on chitosan oligosaccharide6Hydroxyl on position carries out quaternised modified while carrying out quaternization reaction to amino, moreover it is possible to convert amino
At other groups, facilitates and carry out other combination reactions.Secondly, the present invention is anti-using thiosemicarbazides and carbon-to-nitrogen double bon progress addition
It answers, reaction efficiency is high, and other impurities are not generated in reaction process, without being separated.The N- thiosemicarbazides-of this method preparation
The problem of O- quaternary ammonium salt chitosan oligosaccharide, it is poor to not only solve chitosan oligosaccharide, chitosan derivatives adsorptivity, is easily dissolved corrosion, and
It can be used in acid, neutral, alkaline aqueous solution.Meanwhile its bacteriostasis property is improved, in the absorption and inhibition of metal ion
There is good effect on bacterium.
Preferably, step are as follows:
(1) chitosan oligosaccharide the preparation of N- methylene chitosan oligosaccharide: is prepared into chitosan oligosaccharide aqueous solution, Xiang Suoshu chitosan oligosaccharide aqueous solution
Middle dropwise addition formalin, N- methylene chitosan oligosaccharide can be obtained for a period of time by being stirred at room temperature after being added dropwise；
(2) preparation of N- methylene-O- quaternary ammonium salt chitosan oligosaccharide: the N- methylene chitosan oligosaccharide of step (1) preparation is added to having
It is swollen in solvent, the aqueous solution for adding alkali continues to be swollen, and after heating, the chloro- 2- Hydroxyproyl Trimethyl chlorination of 3- is added
Ammonium can obtain N- methylene-O- quaternary ammonium salt chitosan oligosaccharide after being stirred to react；
(3) synthesis of N- thiosemicarbazides-O- quaternary ammonium salt chitosan oligosaccharide: N- methylene-O- quaternary ammonium salt crust prepared by step (2)
Oligosaccharides is added, and modified chitosan oligosaccharide aqueous solution is made into water, and it is water-soluble that thiosemicarbazides is added into the modified chitosan oligosaccharide aqueous solution
Liquid can obtain N- thiosemicarbazides-O- quaternary ammonium salt chitosan oligosaccharide after a period of time is stirred at room temperature.
Room temperature described herein is the temperature of local environment in preparation process, is 15~35 DEG C.
It is further preferred that the number-average molecular weight of the chitosan oligosaccharide is 200~3000, deacetylation is 80%~95%.
Still more preferably, the number-average molecular weight of the chitosan oligosaccharide is 200~1000, and deacetylation is 90%~95%.The molecule
Chitosan oligosaccharide under amount is water-soluble more preferable, can make the amino and C in chitosan oligosaccharide6The hydroxyl of position sufficiently exposes, to improve shell widow
The modification efficiency of sugar.
It is further preferred that the additional amount of formaldehyde is-NH on-CHO and chitosan oligosaccharide repetitive unit in step (1)2Mole
Than for 1.1:1~1.5:1.It can guarantee that the amino in chitosan oligosaccharide is completely modified.
In order to guarantee amino fully reacting, it is further preferred that the time being stirred at room temperature in step (1) is 4~5h.
In order to obtain pure N- methylene chitosan oligosaccharide, a kind of further preferred N- methylene chitosan oligosaccharide of the application it is pure
Change method, the mixed material after step (1) is stirred at room temperature are precipitated using ethyl alcohol, are filtered, and ethanol washing repeatedly carries out afterwards
It is dry.
Still more preferably, the drying is vacuum drying, and dry temperature is 40 DEG C.
It is more abundant in order to be swollen N- methylene chitosan oligosaccharide, preferably by the C in N- methylene chitosan oligosaccharide6The hydroxyl of position
Be exposed, thus carry out it is quaternised modified, the application it is further preferred that organic solvent described in step (2) be isopropanol.
In order to further make the C in N- methylene chitosan oligosaccharide6The hydroxyl of position is fully exposed, the application still more preferably, step
Suddenly it is the NaOH solution that mass fraction is 40% that alkali described in (2), which is aqueous solution,.
In order to accelerate quaternised modified reaction rate, the application is it is further preferred that be heated to 80~85 in step (2)
At DEG C.
In order to make the C in chitosan oligosaccharide6The hydroxyl modification of position is complete, and the application is it is further preferred that state 3- in step (2)
C on chloro-2-hydroxypropyl-trimethyl ammonium chloride and N- methylene chitosan oligosaccharide6The molar ratio of position-OH is 1.1:1~2.5:1.
In order to make the C in chitosan oligosaccharide6The hydroxyl fully reacting of position, the application is it is further preferred that described in step (2)
Being stirred to react the time is 24~36h.
In order to obtain pure N- methylene-O- quaternary ammonium salt chitosan oligosaccharide, a kind of further preferred N- methylene-of the application
The purification process of O- quaternary ammonium salt chitosan oligosaccharide, the mixed material after step (2) is stirred to react are adjusted pH to neutrality, are sunk using acetone
Product filters, then is washed, dried to filter cake.
In order to sufficiently be washed to filter cake, still more preferably, washing is carried out for successively with 80wt.% second to filter cake
Alcohol, 90wt.% ethyl alcohol and dehydrated alcohol are washed.
Still more preferably, the drying is vacuum drying, and dry temperature is 40 DEG C.
In order to make-N=CH2It is modified completely, the application is it is further preferred that thiosemicarbazides and N- methylene-in step (3)
- N=CH on O- quaternary ammonium salt chitosan oligosaccharide2Molar ratio be 1:1~2:1.
In order to guarantee-N=CH2Fully reacting, the application it is further preferred that the time being stirred at room temperature in step (3) be
12~14h.
In order to obtain pure N- methylene chitosan oligosaccharide, a kind of further preferred N- thiosemicarbazides-O- quaternary ammonium of the application
The purification process of salt chitosan oligosaccharide, the mixed material after step (3) is stirred at room temperature are precipitated using ethyl alcohol, are filtered, and ethyl alcohol is washed
It is dried after washing repeatedly.
Still more preferably, the drying is vacuum drying, and dry temperature is 40 DEG C.
Present invention also provides N- amino prepared by a kind of above-mentioned N- thiosemicarbazides-O- quaternary ammonium salt chitosan oligosaccharide or the above method
Thiocarbamide-O- quaternary ammonium salt chitosan oligosaccharide is inhibiting the application in bacterium or adsorption of metal ions.
Present invention also provides N- amino prepared by a kind of above-mentioned N- thiosemicarbazides-O- quaternary ammonium salt chitosan oligosaccharide or the above method
The application of thiocarbamide-O- quaternary ammonium salt chitosan oligosaccharide in the treatment of waste water.
In order to enable those skilled in the art can clearly understand the technical solution of the application, below with reference to tool
The technical solution of the application is described in detail in the embodiment of body.
Embodiment 1
(1) preparation of N- methylene chitosan oligosaccharide
4g chitosan oligosaccharide is dissolved in 50mL deionized water, and taking concentration is 15% formalin 9.3mL, is added dropwise to above-mentioned
In solution, 4h is stirred.4 times of volume ethanol sedimentations, filter, ethanol washing 2 times, 40 DEG C are dried under vacuum to constant weight.
(2) preparation of N- methylene O- quaternary ammonium salt chitosan oligosaccharide
It weighs the product 2g in (1) after drying to be sufficiently swollen in 30mL isopropanol, the NaOH solution of 10mL 40% is added,
After continuing swelling, 1.32g 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride is added at 80 DEG C, is stirred to react for 24 hours.PH is adjusted into
Property, 4 times of vol acetone sedimentations are filtered, are successively washed with 80wt.%, 90wt.% and dehydrated alcohol, 40 DEG C are dried under vacuum to perseverance
Weight.
(3) synthesis of N- thiosemicarbazides-O- quaternary ammonium salt chitosan oligosaccharide
It weighs the product 2g in (2) after drying to be dissolved in 30mL deionized water, weighs 2.26g thiosemicarbazides and be dissolved in 10mL
It is added to after ionized water in above-mentioned solution, continues to be stirred to react 12h at room temperature.4 times of volume ethanol sedimentations, ethanol washing 2 times,
It filters, 40 DEG C are dried under vacuum to constant weight to get N- thiosemicarbazides-O- quaternary ammonium salt chitosan oligosaccharide.It is denoted as sample I.
Embodiment 2
(1) preparation of N- methylene chitosan oligosaccharide
4g chitosan oligosaccharide is dissolved in 50mL deionized water, and taking concentration is 15% formalin 9.5mL, is added dropwise to above-mentioned
In solution, 4h is stirred.4 times of volume ethanol sedimentations, filter, ethanol washing 2 times, 40 DEG C are dried under vacuum to constant weight.
(2) preparation of N- methylene-O- quaternary ammonium salt chitosan oligosaccharide
It weighs the product 2g in (1) after drying to be sufficiently swollen in 30mL isopropanol, the NaOH solution of 10mL 40% is added,
After continuing swelling, 1.32g 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride is added at 80 DEG C, is stirred to react for 24 hours.PH is adjusted into
Property, 4 times of vol acetone sedimentations are filtered, are successively washed with 80wt.%, 90wt.% and dehydrated alcohol, 40 DEG C are dried under vacuum to perseverance
Weight.
(3) synthesis of N- thiosemicarbazides-O- quaternary ammonium salt chitosan oligosaccharide
It weighs the product 2g in (2) after drying to be dissolved in 30mL deionized water, weighs 3.39g thiosemicarbazides and be dissolved in 10mL
It is added to after ionized water in above-mentioned solution, continues to be stirred to react 12h at room temperature.4 times of volume ethanol sedimentations, ethanol washing 2 times,
It filters, 40 DEG C are dried under vacuum to constant weight to get N- thiosemicarbazides-O- quaternary ammonium salt chitosan oligosaccharide.It is denoted as sample II.
Embodiment 3
(1) preparation of N- methylene chitosan oligosaccharide
4g chitosan oligosaccharide is dissolved in 50mL deionized water, and taking concentration is 15% formalin 10mL, is added dropwise to above-mentioned
In solution, 4h is stirred.4 times of volume ethanol sedimentations, filter, ethanol washing 2 times, 40 DEG C are dried under vacuum to constant weight.
(2) preparation of N- methylene O- quaternary ammonium salt chitosan oligosaccharide
It weighs the product 2g in (1) after drying to be sufficiently swollen in 30mL isopropanol, the NaOH solution of 10mL 40% is added,
After continuing swelling, 1.32g 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride is added at 85 DEG C, is stirred to react for 24 hours.PH is adjusted into
Property, 4 times of vol acetone sedimentations are filtered, are successively washed with 80wt.%, 90wt.% and dehydrated alcohol, 40 DEG C are dried under vacuum to perseverance
Weight.
(3) synthesis of N- thiosemicarbazides-O- quaternary ammonium salt chitosan oligosaccharide
It weighs the product 2g in (2) after drying to be dissolved in 30mL deionized water, weighs 4.52g thiosemicarbazides and be dissolved in 12mL
It is added to after ionized water in above-mentioned solution, continues to be stirred to react 12h at room temperature.4 times of volume ethanol sedimentations, ethanol washing 2 times,
It filters, 40 DEG C are dried under vacuum to constant weight to get N- thiosemicarbazides-O- quaternary ammonium salt chitosan oligosaccharide.It is denoted as sample III.
Embodiment 4
(1) preparation of N- methylene chitosan oligosaccharide
4g chitosan oligosaccharide is dissolved in 50mL deionized water, and taking concentration is 15% formalin 9.5mL, is added dropwise to above-mentioned
In solution, 4h is stirred.4 times of volume ethanol sedimentations, filter, ethanol washing 2 times, 40 DEG C are dried under vacuum to constant weight.
(2) preparation of N- methylene O- quaternary ammonium salt chitosan oligosaccharide
It weighs the product 2g in (1) after drying to be sufficiently swollen in 30mL isopropanol, the NaOH solution of 10mL 40% is added,
After continuing swelling, 2.16g 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride is added at 85 DEG C, is stirred to react for 24 hours.PH is adjusted into
Property, 4 times of vol acetone sedimentations are filtered, are successively washed with 80wt.%, 90wt.% and dehydrated alcohol, 40 DEG C are dried under vacuum to perseverance
Weight.
(3) synthesis of N- thiosemicarbazides-O- quaternary ammonium salt chitosan oligosaccharide
It weighs the product 2g in (2) after drying to be dissolved in 30mL deionized water, weighs 3.39g thiosemicarbazides and be dissolved in 10mL
It is added to after ionized water in above-mentioned solution, continues to be stirred to react 12h at room temperature.4 times of volume ethanol sedimentations, ethanol washing 2 times,
It filters, 40 DEG C are dried under vacuum to constant weight to get N- thiosemicarbazides-O- quaternary ammonium salt chitosan oligosaccharide.It is denoted as sample IV.
Embodiment 5
(1) preparation of N- methylene chitosan oligosaccharide
4g chitosan oligosaccharide is dissolved in 50mL deionized water, and taking concentration is 15% formalin 10mL, is added dropwise to above-mentioned
In solution, 4h is stirred.4 times of volume ethanol sedimentations, filter, ethanol washing 2 times, 40 DEG C are dried under vacuum to constant weight.
(2) preparation of N- methylene O- quaternary ammonium salt chitosan oligosaccharide
It weighs the product 2g in (1) after drying to be sufficiently swollen in 30mL isopropanol, the NaOH solution of 10mL 40% is added,
After continuing swelling, 3.0g 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride is added at 80 DEG C, is stirred to react for 24 hours.PH is adjusted to neutrality,
4 times of vol acetone sedimentations, filter, are successively washed with 80wt.%, 90wt.% and dehydrated alcohol, 40 DEG C are dried under vacuum to constant weight.
(3) synthesis of N- thiosemicarbazides-O- quaternary ammonium salt chitosan oligosaccharide
It weighs the product 2g in (2) after drying to be dissolved in 30mL deionized water, weighs 3.39g thiosemicarbazides and be dissolved in 10mL
Ionized water is added in above-mentioned solution, continues to be stirred to react 12h at room temperature.4 times of volume ethanol sedimentations, ethanol washing 2 times, take out
Filter, 40 DEG C are dried under vacuum to constant weight to get N- thiosemicarbazides-O- quaternary ammonium salt chitosan oligosaccharide.It is denoted as sample V.
The degree of substitution that each embodiment prepares the grafted moiety of sample is as shown in table 1.
The degree of substitution of 1 each sample grafted moiety of table
Heavy metal ion adsorbed test
Method: the preparation of metallic ion mixed liquor, standard metal Ar ion mixing reagent stoste is diluted, wherein containing
Nickel (II) (Ni, 2.0mg/L), copper (II) (Cu, 1.6mg/L), cadmium (II) (Cd, 0.8mg/L), zinc (II) (Zn, 0.8mg/L) and
Lead (II) (Pd, 8.0mg/L).Accurately weigh 50mg sample and 50mg chitosan oligosaccharide (number-average molecular weight be 200~3000, take off
Acetyl degree 85%-90%), it is added to 10mL and contains in the solution of mixed metal ion.With the HNO of 0.1mol/L concentration3With
NaOH adjusts the pH value of solution to 4,7 and 9 three ranges.Then, plastic centrifuge tube is placed on shaking table, (25 DEG C at room temperature
± 0.1 DEG C) place absorption about 36 hours.Separately one group of blank test is done to compare.
After adsorption experiment terminates, by the adsorbent for being adsorbed with metal ion in each sample cell, using membrane filter method
Filtering.Propulsion filtering is carried out using the syringe equipped with 0.10 μm of filter membrane, filtrate is collected.Accurate measurement certain volume
Solution after absorption, is detected.
The absorption test result of sample I, II, III to metal ion when table 2.pH=4
The absorption test result of sample I, II, III to metal ion when table 3.pH=7
The absorption test result of sample I, II, III to metal ion when table 4.pH=9
After tested, flocculating effect is best after N- thiosemicarbazides-O- quaternary ammonium salt chitosan oligosaccharide is contacted with heavy metal ion in water,
Therefore the degree of substitution for changing thiosemicarbazides carries out heavy metal adsorption test, observes test effect.By the data of table 2~4 it is found that
Under different pH environment, the adsorption capacity of sample I, II, III for heavy metal ion Ni (II), Cu (II), Cd (II) and Pb (II)
Difference, and it is preferable to adsorption effect when being adsorbed on pH=7, pH=9 of above-mentioned five metal ion species, this is because in neutral or alkali
Property environment under heavy metal ion easily form precipitating, some sedimentation, remainder is adsorbed, to keep its surplus less,
Wherein with the increase of the degree of substitution of thiosemicarbazides, its adsorption efficiency is higher, but to Zn (II) almost without adsorption capacity,
It is the result because of hydroxide itself precipitation of Zn (II) that concentration, which is reduced, under neutral and alkaline environment.Bacterium minimum is antibacterial
The measurement of concentration
Antibacterial activity test is carried out with minimal inhibitory concentration method, tested strain is transferred and is respectively as follows: staphylococcus aureus, big
Enterobacteria, Pseudomonas aeruginosa, streptococcus, Aeromonas hydrophila, Vibrio flurialis.
It is gently drawn with oese and takes a ring strain bacterium colony to 110mL nutrient broth (peptone 1g, sodium chloride 0.5g, beef
Cream 0.3g, deionized water 110mL, pH=7.0 ± 0.1) in, bacterium colony on 37 DEG C of constant-temperature tables 120r/min culture 20~for 24 hours,
It prepares sterile saline and bacteria suspension is diluted to 3.0 × 106CFU/mL, in case antibacterial test.
Method: (number-average molecular weight is 200,000~500,000 to the chitosan of preparation mass fraction 1%, deacetylation 85%- respectively
90%) ultrasonic disperse Yu Shuizhong, 1% chitosan oligosaccharide (number-average molecular weight be 200~3000, deacetylation 85%-90%) water
The aqueous solution of solution and sample II, IV, V, after 125 DEG C of high-temperature sterilization 30min, the battalion after being dissolved in high-temperature sterilization with 2 times of dilution methods
It supports in meat soup, preparation ultimate density is 0.1,0.05,0.025,0.0125,0.00625,0.00313% solution, takes 0.1mL dense
Degree about 3.0 × 106The bacteria suspension of CFU/mL takes 0.1mL to apply plate, bacterium in the above-mentioned a concentration samples of 0.9mL after concussion uniformly
Suspension obtains minimum inhibitory concentration in 37 DEG C of culture 72h, number bacterium colony.
The minimum inhibitory concentration of chitosan and sample II, IV, V when 5 pH=7 of table
As shown in Table 5, in neutral environment, the bacteriostatic activity of chitosan is very weak, and reason mainly has two o'clock: first is that in neutrality
The solubility of chitosan is very low under environment；Second is that chitosan C in a neutral environment2The protonization level of bit amino is low.And shell is few
The water solubility of sugar very well, compares chitosan, and fungistatic effect significantly improves, but still undesirable.Chitosan oligosaccharide after quaternization, one
Aspect enhances solubility, on the other hand, with the continuous improvement of sample II, IV, V quaternization degree, different degrees of quaternary ammonium
Change makes itself just have positive charge, is easy to interact with electronegative bacterial outer membrane.These two aspects acts on so that N-
The bacteriostatic activity of thiosemicarbazides-O- quaternary ammonium salt chitosan oligosaccharide has significant enhancing.
The foregoing is merely preferred embodiment of the present application, are not intended to limit this application, for the skill of this field
For art personnel, various changes and changes are possible in this application.Within the spirit and principles of this application, made any to repair
Change, equivalent replacement, improvement etc., should be included within the scope of protection of this application.
Claims (13)
1. a kind of N- thiosemicarbazides-O- quaternary ammonium salt chitosan oligosaccharide, characterized in that its structural formula is as follows:
It is by chitosan oligosaccharide through amino and C6The hydroxyl of position is obtained by modified, wherein the number-average molecular weight of the chitosan oligosaccharide is 200
~3000.
2. a kind of preparation method of N- thiosemicarbazides-O- quaternary ammonium salt chitosan oligosaccharide, characterized in that using the ammonia on formaldehyde and chitosan oligosaccharide
Base carries out reaction and obtains N- methylene chitosan oligosaccharide, then using 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride and the N- methylene
C in chitosan oligosaccharide6Hydroxyl on position carries out reaction and obtains N- methylene-O- quaternary ammonium salt chitosan oligosaccharide, finally uses thiosemicarbazides and institute
The carbon-to-nitrogen double bon for stating N- methylene-O- quaternary ammonium salt chitosan oligosaccharide carries out addition reaction and obtains N- thiosemicarbazides-O- quaternary ammonium salt chitosan oligosaccharide.
3. preparation method as claimed in claim 2, characterized in that step are as follows:
(1) preparation of N- methylene chitosan oligosaccharide: chitosan oligosaccharide is prepared into chitosan oligosaccharide aqueous solution, is dripped in Xiang Suoshu chitosan oligosaccharide aqueous solution
Add formalin, N- methylene chitosan oligosaccharide can be obtained for a period of time by being stirred at room temperature after being added dropwise；
(2) preparation of N- methylene-O- quaternary ammonium salt chitosan oligosaccharide: the N- methylene chitosan oligosaccharide of step (1) preparation is added to organic molten
It is swollen in agent, the aqueous solution for adding alkali continues to be swollen, and after heating, 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride is added, stirs
N- methylene-O- quaternary ammonium salt chitosan oligosaccharide can be obtained after mixing reaction；
(3) synthesis of N- thiosemicarbazides-O- quaternary ammonium salt chitosan oligosaccharide: N- methylene-O- quaternary ammonium salt chitosan oligosaccharide prepared by step (2)
Modified chitosan oligosaccharide aqueous solution is made into water for addition, and thiosemicarbazides aqueous solution, room are added into the modified chitosan oligosaccharide aqueous solution
Temperature can obtain N- thiosemicarbazides-O- quaternary ammonium salt chitosan oligosaccharide after stirring a period of time.
4. preparation method as claimed in claim 3, characterized in that the number-average molecular weight of the chitosan oligosaccharide is 200~3000, is taken off
Acetyl degree is 80%~95%.
5. preparation method as claimed in claim 4, characterized in that it is preferred, the number-average molecular weight of the chitosan oligosaccharide is 200~
1000, deacetylation is 90%~95%.
6. preparation method as claimed in claim 3, characterized in that the additional amount of formaldehyde is-CHO and chitosan oligosaccharide in step (1)
- NH on repetitive unit2Molar ratio be 1.1:1~1.5:1.
7. preparation method as claimed in claim 3, characterized in that organic solvent described in step (2) is isopropanol.
8. preparation method as claimed in claim 3, characterized in that alkali described in step (2) is that aqueous solution is that mass fraction is
40% NaOH solution.
9. preparation method as claimed in claim 3, characterized in that step is heated to 80~85 DEG C in (2).
10. preparation method as claimed in claim 3, characterized in that state the chloro- 2- Hydroxyproyl Trimethyl chlorination of 3- in step (2)
C on ammonium and N- methylene chitosan oligosaccharide6The molar ratio of position-OH is 1.1:1~2.5:1.
11. preparation method as claimed in claim 3, characterized in that thiosemicarbazides and N- methylene-O- quaternary ammonium in step (3)
- N=CH on salt chitosan oligosaccharide2Molar ratio be 1:1~2:1.
12. a kind of N- thiosemicarbazides-O- quaternary ammonium salt chitosan oligosaccharide described in claim 1 or claim 2~11 are any described
N- thiosemicarbazides-O- quaternary ammonium salt the chitosan oligosaccharide of preparation method preparation is inhibiting the application in bacterium or adsorption of metal ions.
13. a kind of N- thiosemicarbazides-O- quaternary ammonium salt chitosan oligosaccharide described in claim 1 or claim 2~11 are any described
The application of the N- thiosemicarbazides-O- quaternary ammonium salt chitosan oligosaccharide of preparation method preparation in the treatment of waste water.
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