CN107129543B - A kind of thiocarbamide modification of chitosan and its preparation method and application - Google Patents
A kind of thiocarbamide modification of chitosan and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of thiocarbamide modification of chitosan, preparation method includes: that (1) dissolves the chitosan in acetic acid solution, and glutaraldehyde water solution is added, cross-linking modified chitosan is reacted to obtain under microwave radiation；(2) the cross-linking modified chitosan that step (1) obtains is soaked in NaOH aqueous solution, monoxone is added, monoxone modification of chitosan is reacted to obtain under microwave radiation；Thiocarbamide is then added, 0.5~1.5h is reacted under microwave radiation, the thiocarbamide modification of chitosan is obtained after being filtered, being washed.The present invention is using chitosan as parent, it is reacted with ligand thiocarbamide, the thiocarbamide modification of chitosan with high function base conversion ratio can be obtained under microwave action, gained thiocarbamide modification of chitosan has good selectivity absorption property to food synthetic pigment, can apply to the analysis detection field of amaranth in beverage.
Description
Technical field
The invention belongs to edible synthesized coloring matters to adsorb detection field, and in particular to a kind of thiocarbamide modification of chitosan and its preparation
Methods and applications.
Background technique
Edible pigment can be divided into edible natural pigment and secondary colour as the food additives for improving sensory quality of food
Element.Edible natural pigment is extracted from animal and plant, usually relatively safety, harmless, but there are dyeing capacities poor, ingredient
The disadvantages of complexity, stability is poor, easy to change, higher cost limits its application in the food industry.Edible synthesized coloring matter
Synthesis processing is carried out by Organic Chemicals to obtain, and has tinting strength, tinting power high, bright in colour, impurity is less, high stability, easily
The advantages that storage, price is lower, it is widely used in food.But edible synthesized coloring matter has certain toxic effect, mainly
It is that different journeys are caused to human body due to heavy metal therein (lead, copper, arsenic), ether, phenol, aniline, chloride and sulfate etc.
The harm of degree.
In recent years, edible synthesized coloring matter dosage in China's is in cumulative year after year, and in the case where interests drive, breakthrough allows to make criminal
Kind, quantity and range abuse edible synthesized coloring matter, so that food safety violation event frequently occurs, threaten consumption
The health of person, food safety face the challenge.The measurement of so edible synthesized coloring matter has become the pass for guaranteeing food safety
Key.
There is high performance liquid chromatography to the common detection method of edible synthesized coloring matter at present, high performance capillary electrophoresis, divide
Light photometry, fluorescent spectrometry, thin-layered chromatography etc..High performance liquid chromatography high sensitivity, precision is high, good separating effect,
Amount of samples is less, and detection limit is lower, but the method pretreatment process is cumbersome, and mobile phase and is needed more with toxic organic solvents
Kind solvent makees mobile phase, easily causes environmental pollution, and experiment process is slower, and operation is more demanding, and solvent.Equipment is costly.
And high performance capillary electrophoresis is easy to operate, and separating rate is fast, and reagent consumption is less, to the of reduced contamination of environment generation, but point
It is weaker from ability, to the more demanding of pH value.Polarography is applied widely, the range that can measure constituent content is wide, accuracy is high,
High sensitivity, precision is good, favorable reproducibility, selectivity are strong, can carry out METHOD FOR CONTINUOUS DETERMINATION, but its preparation trouble, dropping-mercury electrode requirement
Strictly, mercury is volatile and mercury vapour is toxic, not yet universal in inspection body, base.So edible synthesized coloring matter in food
There is instrument and equipment valuableness in determination method, at high cost, vulnerable to interference, applicable food narrow range is cumbersome etc. mostly
Disadvantage.
Chitosan has good biocompatibility and adsorptivity, and nontoxic because having, and chemical property is stablized, can be biological
The characteristics such as degradation, are widely used in the fields such as biotechnology, chemical industry, light and textile industries, food industry.Modification of chitosan can be made
For it is a kind of it is high absorption, low cost adsorbent, adsorpting pigment, in terms of be of wide application it is general.
Microwave is one kind of electromagnetic wave, and between shortwave and far infrared, wavelength is from 1mm-1m, referred to as microwave, frequency
About in 300MHz to being widely used in medical treatment, scientific research, industrial or agricultural and daily life between 300GHz.Microwave spoke
It penetrates method to compare with conventional heating methods, heating method is internal heating, does not need media heat transfer, has aggregate velocity fast, instead
Short, simple operation and other advantages between seasonable.Therefore, before microwave heating technique has good application development in the field of chemical synthesis
Scape.
Microwave heating is modified chitosan, is more advantageous to the progress of synthetic reaction, and have reaction speed fast and
Homogeneous heating, energy-efficient, easily controllable, the advantages that environmental pollution is less.The method is available more for advantageous property
Modification of chitosan.
Summary of the invention
The purpose of invention is to solve above-mentioned technology existing in the prior art and cost problem, and it is modified to provide a kind of thiocarbamide
Chitosan and its preparation method and application, the present invention are reacted using cross-linked chitosan as parent with ligand thiocarbamide, are made in microwave
The thiocarbamide modification of chitosan with higher functionality base conversion ratio can be obtained with lower, gained thiocarbamide modification of chitosan synthesizes food
Pigment has good selectivity absorption property, can apply to the analysis detection field of amaranth in beverage.
To solve above-mentioned technical problem, the invention adopts the following technical scheme:
A kind of thiocarbamide modification of chitosan has the structure as shown in formula (I):
In formula, n=1,2,3 ...；
The thiocarbamide modification of chitosan by chitosan is through glutaraldehyde, monoxone and thiocarbamide is modified obtains, chitosan it is de-
Acetyl degree is 80%~95%；Viscosity is 50~800mPas.
The present invention also provides a kind of preparation methods of thiocarbamide modification of chitosan, comprising:
(1) it the microwave synthesis of cross-linking modified chitosan: dissolves the chitosan in acetic acid solution, it is water-soluble that glutaraldehyde is added
Liquid reacts 0.5~1.5h under microwave radiation in 15~35 DEG C and obtains cross-linking modified chitosan；
(2) the cross-linking modified chitosan that step (1) obtains the microwave synthesis of thiocarbamide modification of chitosan: is soaked in NaOH water
In solution, monoxone is added, reacts 0.5~1.5h under microwave radiation in 25~45 DEG C and obtains monoxone modification of chitosan；Then
Thiocarbamide is added, reacts 0.5~1.5h under microwave radiation in 25~45 DEG C, it is poly- that the modified shell of the thiocarbamide is obtained after being filtered, being washed
Sugar.
Preferably, the intrinsic viscosity of the chitosan is 50~800mPas.
Preferably, in step (1), the mass fraction of acetic acid solution is 1~5%, and 30~70mL is added in every gram of chitosan
Acetic acid solution.
Preferably, in step (1), the mass fraction of glutaraldehyde water solution is 20~30%, it is added 1 in every gram of chitosan~
2mL glutaraldehyde water solution.
Preferably, in step (1), the microwave irradiation power is 300~500W.
Preferably, in step (2), the mass fraction of the NaOH aqueous solution is that the dosage of 3~7%, NaOH aqueous solution can
It is adjusted according to the actual situation, is subject to and is completely soaked sample.
Preferably, in step (2), chloroacetic dosage is 0.1~0.5 times of chitosan mass in step (1), with
Monoxone adds the increase of ratio, and the function base conversion of thiocarbamide modification of chitosan takes the lead in reducing after increasing.Further preferably, chloroethene
The dosage of acid is 0.2~0.5 times of chitosan mass in step (1).
Preferably, in step (2), reaction temperature is 15~35 DEG C, and within this temperature range, function base conversion ratio is with anti-
It answers the rising of temperature and increases, the raising of temperature facilitates the positive of synthetic reaction and carries out, i.e. temperature is higher, and conversion ratio is higher.
Further preferably, reaction temperature is 25~35 DEG C.
Preferably, in step (2), 1~5:1 of molar ratio of chitosan in thiocarbamide and step (1).The molar ratio of thiocarbamide
When lower, function base conversion ratio becomes larger with the increase of molar ratio, this is because with the raising of ligand concentration so that ligand with
The reaction active site point contact of parent increases, and facilitates the positive of synthetic reaction and carries out, therefore function base conversion ratio also increases；But
After reactivity site has reached saturation state, with continuing growing for molar ratio, hinders the positive of synthetic reaction and carries out,
Significant changes no longer occur substantially for function base conversion ratio.Further preferably, the molar ratio 2~3 of thiocarbamide and step (1) chitosan:
1。
Preferably, in step (2), the microwave irradiation power is 300~500W.
The present invention also provides a kind of application of above-mentioned thiocarbamide modification of chitosan in absorption amaranth.
The present invention also provides a kind of applications of above-mentioned thiocarbamide modification of chitosan analysis detection amaranth in the beverage.This hair
The separation and concentration and context of detection of bright edible synthesized coloring matter in the beverage are widely used, and can have by thiocarbamide modification of chitosan
Edible synthesized coloring matter in the separation and concentration beverage of effect, by being detected with UV-VIS spectrophotometry combination, the method
It is easy to operate, at low cost, precision is high, good separating effect, the rate of recovery are high.
The present invention compared with the existing technology, has the advantages that
1, raw material chitosan of the invention has good biocompatibility and adsorptivity, and nontoxic because having, chemistry
Property is stablized, biodegradable.It is at low cost can and the characteristics such as efficiently concentrating, be widely used in biotechnology chemical industry, light textile
The fields such as industry, food industry.And containing a large amount of active hydroxyls and amino in chitosan macromolecular, to this with strongerization
Respond is learned, it is easily modified, and by surface graft modification, make chitosan can amaranth pigment in enriched food.Meanwhile it closing
At simple to operate, it is more suitable for the detection to food synthetic pigment.
2, the present invention is modified chitosan with microwave irradiation.Compare with traditional heating, when being substantially shorter reaction
Between, accelerate reaction rate, homogeneous heating, and reduce production cost, the more excellent modification of chitosan of available absorption property.
3, thiocarbamide modification of chitosan provided by the invention is recyclable, reusable, can be improved the utilization rate of resource.
Detailed description of the invention
Fig. 1 is that chitosan (CTS), cross-linking modified chitosan (GCTS), monoxone modification of chitosan (CCTS) and thiocarbamide change
The infrared spectrogram of property chitosan microball (TCCTS)；
Fig. 2 is the thermogravimetric curve of chitosan (CTS), thiocarbamide (THU) and thiocarbamide modification of chitosan (TCCTS)；
Fig. 3 is for TCCTS to the absorption property result figure of amaranth solution under condition of different pH；
Fig. 4 is TCCTS at different temperatures to the absorption property result figure of amaranth solution.
Specific embodiment
In the present invention, the method for computing function base conversion ratio (%) is as follows:
1.000~2.000mg thiocarbamide modification of chitosan microballoon is accurately weighed by millionth balance, uses masking foil
It is sequentially placed into pallet after package and waits sample analysis.The modified shell of thiocarbamide is determined using Vario EL type III elemental analyser
The content of N element in glycan microballoon, and it is calculated by the following formula function base conversion ratio in thiocarbamide modification of chitosan microballoon
(functionalgroup conversion, %).
In above formula, x is function base conversion ratio,
F0For amino content in chitosan (mmol/g),
N0For the nitrogen content (%) of chitosan,
NcFor the nitrogen content (%) of thiocarbamide modification of chitosan microballoon,
MLFor the molal weight (g/mol) of ligand,
nNFor the number of nitrogen-atoms in ligand molecular.
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
Embodiment 1
The preparation method of thiocarbamide modification of chitosan of the invention, comprising the following steps:
(1) it takes 0.5g chitosan to be placed in a beaker, 2% acetic acid solvent of 20ml is added, stirring obtains 2% shell to dissolving
Glycan acetic acid solution；25% glutaraldehyde solution of 0.5ml is added and stirs, is placed in microwave reactor, 300W microwave radiation function
Under rate, with the revolving speed heating temperature of 300rmp for 35 DEG C, 1h is stirred.Natural cooling is filtered and is washed for several times, in 50
It is dried in vacuo at DEG C and obtains the cross-linking modified chitosan of intermediate product (GCTS) for 24 hours.
(2) product of step (1) is soaked in after carrying out oscillation 4h in 50ml 5%NaOH solution, the chloroethene of 0.1g is added
Acid is placed in microwave reactor, and under 300W microwave irradiation power, with 300rmp revolving speed, heating stirring is carried out under the conditions of 35 DEG C
Reaction 1h obtains intermediate product monoxone modification of chitosan (CCTS).It is added thiocarbamide (THU), shell in added thiocarbamide and step (1)
The molar ratio of glycan is 2:1, the reaction was continued at 35 DEG C 1h, after obtained product natural cooling, carries out filtering and washing to neutrality.
It is dried in vacuo at 50 DEG C and obtains final product thiocarbamide modification of chitosan (TCCTS) for 24 hours.
Through detecting, the function base conversion ratio of gained thiocarbamide modification of chitosan microballoon is 33.66%.
Gained chitosan (CTS), cross-linking modified chitosan (GCTS), monoxone modification of chitosan (CCTS) and thiocarbamide are modified
The infrared spectrum of chitosan microball (TCCTS) is as shown in Figure 1, from figure 1 it appears that chitosan (CTS) and cross-linking modified shell
3400cm in glycan (GCTS)-1The absorption peak at place is overlapped by the stretching vibration of O-H and N-H, and GCTS is in 1649cm-1Locate C=N
Characteristic absorption peak enhancing, this is because foring schiff bases after glutaraldehyde cross-linking.CCTS is in 1071cm-1The absorption peak at place increases
By force, illustrate C6Changed on-O, in 1601cm-1There is carboxylate radical COO- antisymmetric stretching vibration peak in place, illustrates chloroethene
Acid and C6On hydroxyl reacted.TCCTS is in 1400cm-1The symmetrical stretching vibration peak of the carboxylate radical COO- at place weakens, and says
It is bright to be reacted on carboxyl, and in 1662cm-1There is the stretching vibration absworption peak of C=O in amide, C=S characteristic peak in place
In 1020~1250cm-1, the peak intensity is weaker, and in summary, thiocarbamide is successfully introduced into chitosan.
The thermogravimetric curve of chitosan (CTS), thiocarbamide (THU) and thiocarbamide modification of chitosan (TCCTS) is as shown in Figure 2.Sulphur
Urea (THU), substantially without weightlessness, decomposes rapidly, weight-loss ratio is about between 25 DEG C to 200 DEG C between 200 DEG C to 300 DEG C
89.51%.THU is decomposed slowly until decomposing completely, weight-loss ratio reaches 100% between 300 DEG C to 800 DEG C.Compared with chitosan,
TCCTS is decomposed slowly between 25 DEG C to 245 DEG C, it may be possible to which the evaporation of moisture, weight-loss ratio are about 8.99%.From 245 DEG C to 800 DEG C
Between, TCCTS is first decomposed rapidly, and rear decomposition is slowly up to decomposing completely, about remaining 37.29% ashes and residue, and is greater than CTS
Remaining weight illustrates that TCCTS is modified successfully.TCCTS is resistant to 245 DEG C of temperature below, and thermostabilization is preferable, and 600 DEG C or more can
It decomposes completely, environmental pollution is small.
Embodiment 2
The preparation method of thiocarbamide modification of chitosan of the invention, comprising the following steps:
(1) it takes 0.5g chitosan to be placed in a beaker, 5% acetic acid solvent of 15ml, stirring to dissolution is added；0.5ml is added
25% glutaraldehyde solution simultaneously stirs, and is placed in microwave reactor, under 300W microwave irradiation power, is heated with the revolving speed of 300rmp
Temperature is 35 DEG C, stirs 1h.Natural cooling is filtered and is washed for several times, is dried in vacuo at 50 DEG C and obtain centre for 24 hours
The cross-linking modified chitosan of product (GCTS).
(2) product of step (1) is soaked in after carrying out oscillation 4h in 60ml 5%NaOH solution, the chloroethene of 0.1g is added
Acid is placed in microwave reactor, and under 400W microwave irradiation power, with 300rmp revolving speed, heating stirring is carried out under the conditions of 35 DEG C
Reaction 1h obtains intermediate product monoxone modification of chitosan (CCTS).It is added thiocarbamide (THU), shell in added thiocarbamide and step (1)
The molar ratio of glycan is 2:1, the reaction was continued at 30 DEG C 1h, after obtained product natural cooling, carries out filtering and washing to neutrality.
It is dried in vacuo at 50 DEG C and obtains final product thiocarbamide modification of chitosan (TCCTS) for 24 hours.
Through detecting, the function base conversion ratio of gained thiocarbamide modification of chitosan microballoon is 27.8%.
Embodiment 3
(1) it takes 0.5g chitosan to be placed in a beaker, 1% acetic acid solvent of 35ml, stirring to dissolution is added；1.0ml is added
25% glutaraldehyde solution simultaneously stirs, and is placed in microwave reactor, under 300W microwave irradiation power, is heated with the revolving speed of 300rmp
Temperature is 30 DEG C, stirs 1.5h.Natural cooling is filtered and is washed for several times, is dried in vacuo in obtaining for 24 hours at 50 DEG C
Between the cross-linking modified chitosan of product (GCTS).
(2) product of step (1) is soaked in after carrying out oscillation 4h in 70ml 3%NaOH solution, the chlorine of 0.25g is added
Acetic acid is placed in microwave reactor, under 300W microwave irradiation power, with 300rmp revolving speed, under the conditions of 35 DEG C heating stirring into
Row reaction 1.5h obtains intermediate product monoxone modification of chitosan (CCTS).It is added thiocarbamide (THU), added thiocarbamide and step (1)
The molar ratio of middle chitosan is 3:1, the reaction was continued at 35 DEG C 1h, after obtained product natural cooling, carries out filtering and washing extremely
It is neutral.It is dried in vacuo at 50 DEG C and obtains final product thiocarbamide modification of chitosan (TCCTS) for 24 hours.
Through detecting, the function base conversion ratio of gained thiocarbamide modification of chitosan microballoon is 31.74%.
Embodiment 4
(1) it takes 0.5g chitosan to be placed in a beaker, 3% acetic acid solvent of 20ml, stirring to dissolution is added；1.0ml is added
20% glutaraldehyde solution simultaneously stirs, and is placed in microwave reactor, under 500W microwave irradiation power, is heated with the revolving speed of 300rmp
Temperature is 15 DEG C, stirs 1.5h.Natural cooling is filtered and is washed for several times, is dried in vacuo in obtaining for 24 hours at 50 DEG C
Between the cross-linking modified chitosan of product (GCTS).
(2) product of step (1) is soaked in after carrying out oscillation 5h in 75ml 3%NaOH solution, the chloroethene of 0.2g is added
Acid is placed in microwave reactor, and under 300W microwave irradiation power, with 300rmp revolving speed, heating stirring is carried out under the conditions of 45 DEG C
Reaction 0.5h obtains intermediate product monoxone modification of chitosan (CCTS).It is added thiocarbamide (THU), in added thiocarbamide and step (1)
The molar ratio of chitosan is 3:1, the reaction was continued at 45 DEG C 1h, after obtained product natural cooling, carries out filtering and washing into
Property.It is dried in vacuo at 50 DEG C and obtains final product thiocarbamide modification of chitosan (TCCTS) for 24 hours.
Through detecting, the function base conversion ratio of gained thiocarbamide modification of chitosan microballoon is 32.06%.
Embodiment 5
(1) it takes 0.5g chitosan to be placed in a beaker, 5% acetic acid solvent of 15ml is added, stirring obtains 2% shell to dissolving
Glycan acetic acid solution；20% glutaraldehyde solution of 2ml is added and stirs, is placed in microwave reactor, 500W microwave irradiation power
Under, with the revolving speed heating temperature of 300rmp for 15 DEG C, stir 1.5h.Natural cooling is filtered and is washed for several times, in 50
It is dried in vacuo at DEG C and obtains the cross-linking modified chitosan of intermediate product (GCTS) for 24 hours.
(2) product of step (1) is soaked in after carrying out oscillation 4h in 60ml 3%NaOH solution, the chlorine of 0.05g is added
Acetic acid is placed in microwave reactor, under 500W microwave irradiation power, with 300rmp revolving speed, under the conditions of 40 DEG C heating stirring into
Row reaction 0.5h obtains intermediate product monoxone modification of chitosan (CCTS).It is added thiocarbamide (THU), added thiocarbamide and step (1)
The molar ratio of middle chitosan is 4:1, the reaction was continued at 40 DEG C 0.5h, after obtained product natural cooling, carries out filtering and washing
To neutrality.It is dried in vacuo at 50 DEG C and obtains final product thiocarbamide modification of chitosan (TCCTS) for 24 hours.
Through detecting, the function base conversion ratio of gained thiocarbamide modification of chitosan microballoon is 27.58%.
Embodiment 6
(1) it takes 0.5g chitosan to be placed in a beaker, 2% acetic acid solvent of 20ml is added, stirring obtains 2% shell to dissolving
Glycan acetic acid solution；25% glutaraldehyde solution of 0.5ml is added and stirs, is placed in microwave reactor, 300W microwave radiation function
Under rate, with the revolving speed heating temperature of 300rmp for 35 DEG C, 1h is stirred.Natural cooling is filtered and is washed for several times, in 50
It is dried in vacuo at DEG C and obtains the cross-linking modified chitosan of intermediate product (GCTS) for 24 hours.
(2) product of step (1) is soaked in after carrying out oscillation 4h in 50ml 5%NaOH solution, the chlorine of 0.05g is added
Acetic acid is placed in microwave reactor, under 500W microwave irradiation power, with 300rmp revolving speed, under the conditions of 35 DEG C heating stirring into
Row reaction 0.5h obtains intermediate product monoxone modification of chitosan (CCTS).It is added thiocarbamide (THU), added thiocarbamide and step (1)
The molar ratio of middle chitosan is 1:1, the reaction was continued at 35 DEG C 0.5h, after obtained product natural cooling, carries out filtering and washing
To neutrality.It is dried in vacuo at 50 DEG C and obtains final product thiocarbamide modification of chitosan (TCCTS) for 24 hours.
Through detecting, the function base conversion ratio of gained thiocarbamide modification of chitosan microballoon is 23.75%.
Embodiment 7
(1) it takes 0.5g chitosan to be placed in a beaker, 2% acetic acid solvent of 20ml is added, stirring obtains 2% shell to dissolving
Glycan acetic acid solution；25% glutaraldehyde solution of 0.5ml is added and stirs, is placed in microwave reactor, 300W microwave radiation function
Under rate, with the revolving speed heating temperature of 300rmp for 35 DEG C, 1h is stirred.Natural cooling is filtered and is washed for several times, in 50
It is dried in vacuo at DEG C and obtains the cross-linking modified chitosan of intermediate product (GCTS) for 24 hours.
(2) product of step (1) is soaked in after carrying out oscillation 4h in 50ml 5%NaOH solution, the chlorine of 0.25g is added
Acetic acid is placed in microwave reactor, under 400W microwave irradiation power, with 300rmp revolving speed, under the conditions of 25 DEG C heating stirring into
Row reaction 1.5h obtains intermediate product monoxone modification of chitosan (CCTS).It is added thiocarbamide (THU), added thiocarbamide and step (1)
The molar ratio of middle chitosan is 5:1, the reaction was continued at 30 DEG C 1h, after obtained product natural cooling, carries out filtering and washing extremely
It is neutral.It is dried in vacuo at 50 DEG C and obtains final product thiocarbamide modification of chitosan (TCCTS) for 24 hours.
Through detecting, the function base conversion ratio of gained thiocarbamide modification of chitosan microballoon is 25.13%.
Embodiment 8
(1) it takes 0.5g chitosan to be placed in a beaker, 2% acetic acid solvent of 20ml is added, stirring obtains 2% shell to dissolving
Glycan acetic acid solution；30% glutaraldehyde solution of 0.3ml is added and stirs, is placed in microwave reactor, 300W microwave radiation function
Under rate, with the revolving speed heating temperature of 300rmp for 35 DEG C, 1h is stirred.Natural cooling is filtered and is washed for several times, in 50
It is dried in vacuo at DEG C and obtains the cross-linking modified chitosan of intermediate product (GCTS) for 24 hours.
(2) product of step (1) is soaked in after carrying out oscillation 4h in 50ml 5%NaOH solution, the chlorine of 0.15g is added
Acetic acid is placed in microwave reactor, under 300W microwave irradiation power, with 300rmp revolving speed, under the conditions of 35 DEG C heating stirring into
Row reaction 1h obtains intermediate product monoxone modification of chitosan (CCTS).It is added thiocarbamide (THU), in added thiocarbamide and step (1)
The molar ratio of chitosan is 3:1, the reaction was continued at 30 DEG C 1.5h, after obtained product natural cooling, carries out filtering and washing extremely
It is neutral.It is dried in vacuo at 50 DEG C and obtains final product thiocarbamide modification of chitosan (TCCTS) for 24 hours.
Through detecting, the function base conversion ratio of gained thiocarbamide modification of chitosan microballoon is 31.54%.
Embodiment 9~14
6 parts of 10mg thiocarbamide modification of chitosan are accurately weighed in iodine flask, be separately added into 20mL pH be 1.0,2.0,
3.0,4.0,5.0 and 6.0 acetic acid-sodium acetate (HAc-NaAc) buffer solution makes its swelling, and it is dense that immersion adds 5mL afterwards for 24 hours
Degree is the amaranth solution of 0.1mg/mL, and the solution thiocarbamide modification of chitosan is not added is tested as blank control, in 298K, oscillation
Constant temperature oscillation is up to adsorption equilibrium under the conditions of frequency is 100rmp, and uses UV-VIS spectrophotometry measurement amaranth dense
Degree, the calculation formula of adsorption capacity are as follows:
In formula:
QeThe static saturated adsorption capacity (mg/g) of-thiocarbamide modification of chitosan adsorbent,
C0- amaranth concentration (mg/mL) in preceding solution is adsorbed,
CeAmaranth concentration (mg/mL) in solution after-adsorption equilibrium,
V-adsorbent solution volume (mL),
M-thiocarbamide modification of chitosan adsorbent quality (g).
To the absorption property of amaranth solution, as a result the present embodiment has studied thiocarbamide modification of chitosan under condition of different pH
As shown in figure 3, as seen from the figure, the different pH value of solution are affected to thiocarbamide modification of chitosan absorption amaranth, adsorb
Amount changes with the variation of pH.At low ph conditions, with the raising of pH, thiocarbamide modification of chitosan holds the absorption of amaranth
Amount increases therewith, and optimal adsorption pH is that 3, TCCTS is higher to the adsorption capacity of amaranth, maximal absorptive capacity 533.3mg/
g.In acid condition, be conducive to absorption of the thiocarbamide modification of chitosan to amaranth.This is because in an acidic solution, thiocarbamide changes
- the NH of property chitosan2Protonation, formation-NH3 +, and the sulfonic acid group on amaranth naphthalene nucleus is in an acidic solution then with anion
Form exist, thiocarbamide modification of chitosan adsorbs amaranth by electrostatic interaction.When pH value of solution continues to increase, two kinds of modified shells
The adsorption capacity of glycan decreases.This is because the effect of thiocarbamide modification of chitosan protonated amino gradually decreases, electrostatic is made
With decrease, so that its adsorption capacity reduces.
Embodiment 15~17
The thiocarbamide modification of chitosan adsorbent of three parts of 10mg is weighed in iodine flask, being separately added into 20mL in pH is 3
After being impregnated for 24 hours in HAc-NaAc buffer solution, addition 5mL concentration be 0.1mg/mL amaranth standard solution, respectively 288K,
298K and 308K, constant temperature oscillation is adsorbed under the conditions of frequency of oscillation is 100rmp.A small amount of solution is pipetted at regular time and quantity to be surveyed
Fixed, until remaining amaranth concentration no longer changes in solution, i.e., adsorption experiment reaches balance.
The present embodiment has studied thiocarbamide modification of chitosan at temperature 288K, 298K and 308K to the absorption heating power of amaranth
Property is learned, as a result as shown in figure 4, by map analysis it is found that since amaranth concentration is larger, and thiocarbamide changes in the absorption initial stage
The adsorption site of property chitosan is more, biggish mass transfer force make thiocarbamide modification of chitosan to the rate of adsorption of amaranth compared with
Fastly, therefore as time increases, TCCTS increases the adsorbance of amaranth rapid.But with the further progress of absorption,
The adsorption site of TCCTS is gradually decreasing, and the amaranth concentration in solution is also being gradually reduced, and adsorption space steric hindrance becomes
Greatly, so that the rate of adsorption of TCCTS reduces, finally absorption reaches equilibrium state.TCCTS is to the time of equilibrium adsorption of amaranth
10h.It is also seen that, temperature has a certain impact to the rate of adsorption and adsorbance from figure.As the temperature rises, accordingly
The maximal absorptive capacity on ground, TCCTS also increases, and illustrates that TCCTS is an endothermic process, the liter of temperature to the absorption of amaranth
Height, which is conducive to the positive of absorption, to carry out.
Embodiment 18~20
After thiocarbamide modification of chitosan after adsorption saturation in embodiment 16 is filtered out, the HAc-NaAc buffer for being 3 with pH
It washs for several times and dries respectively with deionized water, NaOH, NH respectively is then added4Cl and NaCl is as strippant, constant temperature oscillation
Amaranth concentration in solution is measured after to desorption balance.Wherein desorption efficiency (E) calculation formula is as follows:
In formula:
CdThe concentration (mg/mL) of amaranth after-desorption balance,
VdThe volume (mL) of-stripping workshop,
V-adsorbent solution volume (mL),
C0The initial concentration (mg/mL) of-absorption phase amaranth,
CeThe equilibrium concentration (mg/mL) of-absorption phase amaranth.
The desorption ability size of thiocarbamide modification of chitosan is to evaluate a key factor of its absorption property quality.Energy of desorption
Regenerability of the size relation of power to thiocarbamide modification of chitosan, the recovery efficiency and practical application value of amaranth, because
This, the present embodiment inquires into the desorption ability of thiocarbamide modification of chitosan, and experimental result is as shown in table 1.
Desorption efficiency of 1 three kinds of the table different strippants to TCCTS
As seen from the above table, the difference of the type and concentration of strippant can have large effect to desorption effect.Right
In the desorption process of amaranth, TCCTS desorption efficiency under the action of the NaOH of 2mol/L is maximum, and the maximum desorption efficiency of TCCTS is
95.4%.
Embodiment 21
In desorption process, strippant may will affect the absorption property of thiocarbamide modification of chitosan.Therefore this experiment with
Strippant of the NaOH of 2mol/L as TCCTS has inquired into the absorption-desorption recycling experiment of thiocarbamide modification of chitosan, weight
Attached-desorption process 5 times is relapsed, calculates its reuse rate, experimental result is shown in Table 2.
The adsorption rate of 2 TCCTS of table
Regeneration tests the results show that after 5 repetitions are tested, TCCTS is to be saturated for the first time to the adsorbance of amaranth
The 78.9% of adsorbance.It can to sum up obtain, TCCTS has preferable power of regeneration and repeat performance.
Claims (5)
1. a kind of preparation method of thiocarbamide modification of chitosan characterized by comprising
(1) the microwave synthesis of cross-linking modified chitosan: dissolving the chitosan in acetic acid solution, glutaraldehyde water solution be added, in
15~35 DEG C are reacted 0.5~1.5h under microwave radiation and obtain cross-linking modified chitosan；The deacetylation of the chitosan is 80%
~95%, viscosity is 50~800mPas；
(2) the cross-linking modified chitosan that step (1) obtains the microwave synthesis of thiocarbamide modification of chitosan: is soaked in NaOH aqueous solution
In, monoxone is added, chloroacetic dosage is 0.1~0.5 times of chitosan mass in step (1), in 25~45 DEG C micro-
0.5~1.5h is reacted under wave radiation obtains monoxone modification of chitosan；Thiocarbamide is then added, in 25~45 DEG C under microwave radiation it is anti-
0.5~1.5h is answered, the thiocarbamide modification of chitosan is obtained after being filtered, being washed；Microwave irradiation power described in this step be 300~
500W。
2. the preparation method of thiocarbamide modification of chitosan according to claim 1, which is characterized in that in step (1), glutaraldehyde
The mass fraction of aqueous solution is 20~30%, and 1~2mL glutaraldehyde water solution is added in every gram of chitosan.
3. a kind of modified shell of thiocarbamide that the preparation method of thiocarbamide modification of chitosan according to claim 1 or 2 is prepared
Glycan.
4. a kind of application of thiocarbamide modification of chitosan according to claim 3 in absorption amaranth.
5. a kind of application of thiocarbamide modification of chitosan according to claim 3 analysis detection amaranth in the beverage.
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