CN106977977B - A method of synthesis gardenia blue pigment - Google Patents
A method of synthesis gardenia blue pigment Download PDFInfo
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- CN106977977B CN106977977B CN201710213766.1A CN201710213766A CN106977977B CN 106977977 B CN106977977 B CN 106977977B CN 201710213766 A CN201710213766 A CN 201710213766A CN 106977977 B CN106977977 B CN 106977977B
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- blue pigment
- gardenia blue
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B61/00—Dyes of natural origin prepared from natural sources, e.g. vegetable sources
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Abstract
The invention discloses a kind of methods for synthesizing gardenia blue pigment, and this method is first to mix genipin solution with amino acid solution, are then placed under microwave again and set reaction time, temperature and power, gardenia blue pigment solution can be obtained.The present invention has many advantages, such as that combined coefficient is high, generated time is short, product color value is high.
Description
Technical field
The invention belongs to pigment preparation technical fields, and in particular to a method of synthesis gardenia blue pigment.
Background technique
Since the toxic side effect of synthetic dyestuff now on the market becomes clear day by day, safe and non-toxic natural pigment will gradually be accounted for
According to leading market position.And in numerous natural pigments, reacted by Geniposide with amino acid the gardenia blue pigment of preparation due to
Its dissolubility is good, strong coloring force, it is insensitive to photo-thermal the features such as become the focus of people's research.
However current preparation method is usually hydro-thermal method, but there are following technical problems for hydro-thermal method: traditional water-bath adds
Thermal synthesis method needs to complete the synthesis of gardenia blue pigment for 24 hours, and the consumed time is longer, is unfavorable for the life of gardenia blue pigment
It produces.And its sintetics color value is relatively low.
Summary of the invention
In view of the above shortcomings of the prior art, the present invention provides that a kind of combined coefficient is high, generated time is short and product
The method of the high synthesis gardenia blue pigment of color value.
To achieve the goals above, The technical solution adopted by the invention is as follows:
A method of synthesis gardenia blue pigment is first to mix genipin solution with amino acid solution, is then placed in again
The setting of deadline, temperature and power in microwave synthesizer, can be obtained gardenia blue pigment solution after the reaction was completed.
Specifically includes the following steps:
1) first genipin solution is mixed into amino acid solution and reacts stoste, wherein the mass ratio of Geniposide and amino acid
For 2:1~5.
2) then mixed solution obtained in step 1) is placed in microwave synthesizer, corresponding temperature, power is set, instead
5~25min is answered to get gardenia blue pigment solution is arrived.Being added, there is the basic amino acid of side-chain amino group to be polymerize with Geniposide
It should can obtain gardenia blue pigment.
Further include step 3): the gardenia blue pigment solution that step 2) is obtained dilutes 10 times, then scans in 500~700nm
Ultraviolet spectra simultaneously calculates its color value.
Color value is calculated as follows:
Wherein: E is color value value；A is solution in the absorbance value of maximum absorption wave strong point；M is sample quality；F is dilution
Multiple, when undiluted, f=1.
Wherein: the power of microwave described in step 2) is 150W.
The amino acid solution is alanine, glycine, arginine, lysine and histidine solution.This five kinds of amino
Acid is all the basic amino acid with side-chain amino group, can obtain gardenia blue pigment with Geniposide polymerization reaction.Due to smart ammonia
Acid is best as the gardenia blue pigment color value of Material synthesis, and it is advantageous to arginine.
Set temperature described in step 2) is 40~120 DEG C, preferably 100 DEG C.Different temperatures is to reaction time and system
The quality of product have an impact.The raising of temperature, anakmetomeres number increases in reaction solution, and effective collision increases, and reaction rate adds
Fastly, so as to cause the generation of more gardenia blue pigments, but when the temperature is excessively high, prolonged high temperature can be to gardenia blue pigment
Structure damage, the reduction of product color value instead, it is therefore necessary to which reaction temperature condition is optimized.
The mass ratio of amino acid described in step 1) and Geniposide is 2:1.Gardenia blue pigment made from mass ratio difference
Color value it is different.The mass ratio of reactant is too low, will lead to reaction not exclusively, the product quality being prepared is lower, mass ratio
It is excessively high that it will cause wastage of material.
In addition, when the reaction time is 20min, just reaction is completed by experiment, time and the energy are saved.
The amino acid calculates color value using following methods, and step includes:
(1) concentration step 2) it obtained gardenia blue pigment solution and is dried in vacuo, obtain solid-state gardenia blue pigment powder；
(2) the gardenia blue pigment solution of the solid-state gardenia blue pigment powder configuration 0.1mg/mL obtained using step (1), and
It is compared with standard color comparison card, qualitatively judges its colour generation；
(3) the gardenia blue pigment solution that step (2) are prepared is scanned under 500~700nm ultraviolet spectra, and calculates color
Valence,
Color value is calculated as follows:
Wherein: E is color value value；A is solution in the absorbance value of maximum absorption wave strong point；M is sample quality；F is dilution
Multiple, when undiluted, f=1.
It is prepared for respectively with the microwave process for synthesizing in traditional water bath heating and this right respectively by control variate method
Gardenia blue pigment finds the gardenia blue pigment synthesized by microwave process for synthesizing relative to the gardenia blue synthesized by water bath heating
Its absorbance value of pigment, which is substantially all, improves 10% or so.Show that its color value is higher, colorability is stronger.This may be because
Caused by the advantages that microwave synthesis temperature is uniform, the same outside and inside, is quick on the draw.Simultaneously relative to traditional heating water bath synthetic method
Need to complete the synthesis of gardenia blue pigment for 24 hours, microwave process for synthesizing only needs 15min just can complete to react, this is substantially reduced
The time required to synthesis, energy consumption is reduced, combined coefficient is improved.
Compared with prior art, the invention has the following beneficial effects:
1, gardenia blue pigment combined coefficient greatly improves.It for 24 hours could be complete relative to traditional heating water bath synthetic method needs
At the synthesis of gardenia blue pigment, microwave process for synthesizing most only needs 15min just can complete to react fastly, this substantially reduces synthesis and is taken
Between, energy consumption is reduced, combined coefficient is improved.
2, product color value is high.It is synthesized respectively with the microwave in traditional water bath heating and this right by control variate method
Method is prepared for gardenia blue pigment respectively, finds the gardenia blue pigment synthesized by microwave process for synthesizing relative to passing through water bath heating
Its absorbance value of the gardenia blue pigment of synthesis, which is substantially all, improves 10% or so.Show that its color value is higher, colorability is stronger.
Detailed description of the invention
Fig. 1 is each gardenia blue pigment solution of example three in maximum absorption wave strong point absorbance value curve graph；
Fig. 2 is each gardenia blue pigment solution of example four in maximum absorption wave strong point absorbance value curve graph；
Fig. 3 is each gardenia blue pigment solution of example five in maximum absorption wave strong point absorbance value curve graph；
Specific embodiment
Invention is further described in detail combined with specific embodiments below.
Raw material and equipment used are as shown in table 1 in the examples below:
1 raw material of table and equipment source table
| Raw material or equipment | Supplier |
| Alanine | Beijing Suo Laibao Co., Ltd |
| Glycine | Beijing Chuan Xiu Science and Technology Ltd. |
| Arginine | Shanghai Aladdin biochemical technology limited liability company |
| Lysine | Beijing North dawn membrane separation technique company |
| Histidine | Shanghai Shen An instrument factory |
| Microwave synthesizer | Pei An company, the U.S. |
| Digital display thermostat water bath | High honour instrument manufacturing Co., Ltd, Jintan City |
| Dual-beam ultraviolet-uisible spectrophotometer | Beijing Pu Xi all purpose instrument Co., Ltd |
Embodiment one
Microwave synthesis: 5 parts of genipin solution that 2mL concentration is 2mg/mL are measured and is separately added into microwave reaction pipe, respectively
It is anti-that alanine, glycine, arginine, lysine, the histidine solution that measurement 4mL concentration is 2mg/mL are separately added into above-mentioned microwave
Ying Guan sets power 150W, and microwave synthesizes 15min at 80 DEG C, obtains 5 parts of gardenia blue pigment solution.
Heating water bath synthesis: 5 parts of genipin solution that 2mL concentration is 2mg/mL are measured and is separately added into 5 20mL conical flasks
In, it then measures alanine, glycine, arginine, lysine, histidine solution that 4mL concentration is 2mg/mL and is separately added into
Conical flask is stated, 80 DEG C of water-bath concussions for 24 hours, obtain 5 parts of gardenia blue pigment solution.
Detection and calculate: by the gardenia blue pigment solution that is synthesized with heating water bath of microwave synthesis respectively after 10 times of dilution in
500~700nm scans ultraviolet spectra, and the results are shown in Table 2:
The comparison of 2 two kinds of synthetic methods of table
According to upper table it is found that, as synthetic material, selecting different synthetic methods, synthesis obtains for monoamino-acid
Gardenia blue pigment maximum absorption wavelength position be it is identical, show that two methods are suitable for the synthesis of gardenia blue pigment,
But the absorbance value of the gardenia blue pigment synthesized by microwave process for synthesizing is substantially higher in the Cape jasmine synthesized by water bath heating
Caused by the advantages that sub- cyanine, its temperature is uniform when this may be because of microwave synthesis, the same outside and inside, is quick on the draw.Simultaneously
Need to complete the synthesis of gardenia blue pigment for 24 hours relative to traditional heating water bath synthetic method, microwave process for synthesizing only needs 15min
Just it can complete to react, the time required to this substantially reduces synthesis, reduce energy consumption, improve combined coefficient.Therefore microwave is selected
Synthetic method prepares gardenia blue pigment with preferable advantage.
Embodiment two
It measures 5 parts of genipin solution that 2mL concentration is 2mg/mL to be separately added into microwave reaction pipe, it is dense then to measure 4mL
Degree is that alanine, glycine, arginine, lysine, the histidine solution of 2mg/mL is separately added into above-mentioned microwave reaction pipe, is set
Power 150W, microwave synthesizes 15min at 80 DEG C.Gardenia blue pigment after microwave is synthesized through different aminoacids and Geniposide preparation
It is dried in vacuo after concentration, obtains solid state powder.
The gardenia blue pigment solution that concentration is 0.1mg/mL is respectively configured using above-mentioned powder, observes each pigment solution colour
Situation, and it is compared with standard color comparison card, judge colour generation.Then each pigment solution is scanned in 500~700nm ultraviolet
Spectrum calculates color value, while measuring its corresponding L, a, b value with spectrophotometric color measurement instrument, as shown in table 3.
Influence of 3 amino acid classes of table to synthesis gardenia blue pigment
| Amino acid classes | L | a | b | λmax | Color value | Colour generation |
| Arginine | 59.203 | -2.86 | -31.468 | 592 | 83.8 | It is sea blue |
| Lysine | 50.616 | 21.08 | -36.5 | 587 | 112.8 | Royal purple |
| Glycine | 40.16 | 32.35 | -42.2 | 586 | 139.5 | Royal purple |
| Alanine | 60.08 | 13.7 | -31.7 | 588 | 80.7 | Royal purple |
| Histidine | 69.76 | 3.577 | -22.5 | 592 | 57.4 | It is sea blue |
According to gardenia blue pigment colouration mechanism, different aminoacids react the maximum of the gardenia blue pigment of preparation with Geniposide and inhale
Receiving peak position might not be consistent, but it is general all can be within the scope of 585~610nm, and gardenia blue pigment absorption maximum
The peak position the mobile to long wave length direction, shows that its quality is better, color is distincter, and colour generation is closer to beautiful blue, therefore
Generally it is considered that gardenia blue pigment of the absorption peak greater than 590nm is qualified products.As can be seen from the table, arginine, group
The gardenia blue pigment maximum absorption wavelength that propylhomoserin is synthesized with Geniposide has reached at 592nm, is qualified gardenia blue pigment, and its
The maximum absorption peak for the gardenia blue pigment that its amino acid is synthesized with Geniposide is below 590nm, not up to qualified cape jasmine blue
The standard of element.Therefore in order to guarantee preparation gardenia blue pigment colour generation quality, we should select with arginine, histidine with
Geniposide reaction prepares gardenia blue pigment.
The height of pigment color value determines the power of its colorability, and the higher colorability for showing the pigment of color value is more
By force.From the point of view of color value angle, lysine, glycine, alanine and the gardenia blue pigment color value of Geniposide preparation are higher, still
Its absorption maximum peak position and colour generation do not meet the standard of qualified gardenia blue pigment, and histidine reacts preparation with Geniposide
Although gardenia blue pigment complies with standard, but its color value only 57.4, and colorability is poor, therefore they are not ideal gardenia blues
Pigment synthesis raw material.Arginine and the gardenia blue pigment color value of Geniposide preparation have reached 83.8, have stronger colorability,
And its standard for also complying with qualified gardenia blue pigment, this, which has further proved us, should select arginine as raw material and capital Buddhist nun
Gardenia blue pigment should be prepared by redressing.
Embodiment three
It measures 5 parts of genipin solution that 2mL concentration is 2mg/mL to be separately added into microwave reaction pipe, then is separately added into 4mL
Concentration be 2mg/mL arginine solution, synthesis temperature be 80 DEG C, be set separately the reaction time be 5min, 10min, 15min,
20min, 25min, then extract reaction solution 10 times of maximum absorption wave strong point measurement absorbance values of dilution, and result is as shown in Figure 1.
As shown in Figure 1, within 5~20min period, the increase of generated time at any time, the absorbance value of reaction solution is gradually
It increases, analysis reason may be because the increase of generated time, more arginine polymerize to obtain gardenia blue with Geniposide at any time
Pigment, therefore the absorbance value of reaction solution can gradually increase.But after the microwave time being higher than 20min, the absorbance of reaction solution
There is the case where reducing by a small margin in value, this may be to damage because of prolonged high temperature to the structure of gardenia blue pigment,
So as to cause the reduction of the absorbance of reaction solution.In conclusion the generated time of microwave synthesis gardenia blue pigment should select
20min。
Example IV
It measures 5 parts of genipin solution that 2mL concentration is 2mg/mL to be separately added into microwave reaction pipe, then is separately added into 4mL
Concentration is the arginine solution of 2mg/mL, reacts 20min at being respectively 40 DEG C, 60 DEG C, 80 DEG C, 100 DEG C, 120 DEG C in temperature, with
After extract reaction solution dilution 10 times of maximum absorption wave strong points measurement absorbance values, result is as shown in Figure 2.
As shown in Figure 2, being gradually increasing with temperature, the appearance of reaction solution absorbance value first increase the case where reducing afterwards,
In reach highest at 100 DEG C, up to 0.882.This may be because just having started as the temperature rises, to activate in reaction solution
Molecular number increases, and effective collision increases, and reaction rate is accelerated, and so as to cause the synthesis of more gardenia blue pigments, therefore reacts
The absorbance value of liquid can gradually increase, but when the temperature is excessively high, prolonged high temperature can cause the structure of gardenia blue pigment
It destroys, has instead resulted in the reduction of reaction solution absorbance value.Therefore the synthesis temperature of microwave synthesis gardenia blue pigment should select 100
℃。
Embodiment five
5 parts of genipin solution that 2mL concentration is 2mg/mL are measured respectively to be separately added into microwave reaction pipe, then are separately added into
4mL concentration is the arginine solution of 1mg/mL, 2mg/mL, 3mg/mL, 4mg/mL, 5mg/mL, under conditions of temperature is 100 DEG C
20min is reacted, 10 times of maximum absorption wave strong point measurement absorbance values of dilution, concrete outcome such as Fig. 3 institute are then extracted reaction solution
Show.
From the figure 3, it may be seen that with the rising of arginine and Geniposide mass ratio, the suction of gardenia blue pigment in scope of experiment
Shading value occurs first increasing the case where reducing afterwards, reaches maximum when the two mass ratio reaches 2:1, up to 0.879, is
Keep the color value of gardenia blue pigment obtained higher, therefore microwave synthesis gardenia blue pigment arginine should be selected with Geniposide mass ratio
Select 2:1.
The above embodiment of the present invention is only example to illustrate the invention, and is not to implementation of the invention
The restriction of mode.For those of ordinary skill in the art, other can also be made not on the basis of the above description
With the variation and variation of form.Here all embodiments can not be exhaustive.It is all to belong to technical solution of the present invention
Changes and variations that derived from are still in the scope of protection of the present invention.
Claims (5)
1. a kind of method for synthesizing gardenia blue pigment, which is characterized in that first mix genipin solution with amino acid solution, then
The setting that reaction time, reaction temperature and microwave power are completed by microwave synthesizer, can be obtained cape jasmine after the reaction was completed
Cyanine solution；
Specifically includes the following steps:
1) first genipin solution is mixed into amino acid solution and reacts stoste, wherein the mass ratio of Geniposide and amino acid is 2:
1~5；The amino acid solution is arginine solution；
2) then the reaction stoste that step 1) obtains is placed in microwave synthesizer, sets reaction temperature as 40~120 DEG C, microwave
Power is 150W, and 5~25min of reaction time is to get arriving gardenia blue pigment solution.
2. the method for synthesis gardenia blue pigment according to claim 1, which is characterized in that further include step 3): by step
2) the gardenia blue pigment solution obtained dilutes 10 times, then scans ultraviolet spectra in 500~700nm.
3. the method for synthesis gardenia blue pigment according to claim 1, which is characterized in that amino acid described in step 1)
It is 2:1 with Geniposide mass ratio.
4. the method for synthesis gardenia blue pigment according to claim 1, which is characterized in that setting temperature described in step 2)
Degree is 100 DEG C.
5. the method for synthesis gardenia blue pigment according to claim 1, which is characterized in that the amino acid is using following
Method calculates color value, and step includes:
(1) concentration step 2) it obtained gardenia blue pigment solution and is dried in vacuo, obtain solid-state gardenia blue pigment powder；
(2) the gardenia blue pigment solution of the solid-state gardenia blue pigment powder configuration 0.1mg/mL obtained using step (1), and with mark
Quasi- colorimetric card compares, and qualitatively judges its colour generation；
(3) the gardenia blue pigment solution that step (2) are prepared is scanned under 500~700nm ultraviolet spectra, and calculates color value, color
Valence is calculated as follows:
Wherein: E is color value value；A is solution in the absorbance value of maximum absorption wave strong point；M is sample quality；F is extension rate,
When undiluted, f=1.
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