CN106977977A - A kind of method for synthesizing gardenia blue pigment - Google Patents
A kind of method for synthesizing gardenia blue pigment Download PDFInfo
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- CN106977977A CN106977977A CN201710213766.1A CN201710213766A CN106977977A CN 106977977 A CN106977977 A CN 106977977A CN 201710213766 A CN201710213766 A CN 201710213766A CN 106977977 A CN106977977 A CN 106977977A
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- blue pigment
- gardenia blue
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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
- 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 method for synthesizing gardenia blue pigment, this method is first to mix genipin solution with Freamine Ⅲ, is then placed in again under microwave and sets reaction time, temperature and power, you can obtains gardenia blue pigment solution.The present invention has the advantages that combined coefficient is high, generated time is short, product color value is high.
Description
Technical field
The invention belongs to pigment preparing technical field, and in particular to a kind of method of synthesis gardenia blue pigment.
Background technology
Because the toxic side effect of synthetic dyestuff now on the market becomes clear day by day, the natural pigment of safety non-toxic will gradually be accounted for
According to leading market position.And in numerous natural pigments, the gardenia blue pigment prepared by Geniposide and amino acid reaction due to
Its dissolubility is good, strong coloring force, the focus studied the features such as insensitive as people photo-thermal.
But current preparation method is usually hydro-thermal method, but there is following technical problem in hydro-thermal method：Traditional water-bath adds
Thermal synthesis method needs 24h to complete the synthesis of gardenia blue pigment, and the time consumed is longer, is unfavorable for the life of gardenia blue pigment
Production.And its sintetics color value is relatively low.
The content of the invention
For deficiencies of the prior art, a kind of combined coefficient of present invention offer is high, generated time is short and product
The method of the high synthesis gardenia blue pigment of color value.
To achieve these goals, the technical solution adopted by the present invention is as follows：
A kind of method for synthesizing gardenia blue pigment, is first to mix genipin solution with Freamine Ⅲ, is then placed in again
The setting of deadline, temperature and power in microwave synthesizer, gardenia blue pigment solution is can obtain after the completion of reaction.
Specifically include following steps：
1) genipin solution and Freamine Ⅲ are first mixed into the mass ratio of reaction stoste, wherein Geniposide and amino acid
For 2：1~5.
2) mixed solution obtained in and then by step 1) is placed in microwave synthesizer, sets corresponding temperature, power, instead
5~25min is answered, that is, obtains gardenia blue pigment solution.The basic amino acid with side-chain amino group is added with Geniposide to be polymerize
It should can obtain gardenia blue pigment.
Also include step 3)：By step 2) obtained gardenia blue pigment solution dilutes 10 times, then in 500~700nm scannings
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 of maximum absorption wave strong point；M is sample quality；F is dilution
Multiple, when undiluted, f=1.
Wherein：Step 2) described in microwave power be 150W.
Described Freamine Ⅲ 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 polymerisation.Due to smart ammonia
Acid is best as the gardenia blue pigment color value of Material synthesis, and it is advantageous to arginine.
Step 2) described in design temperature be 40~120 DEG C, preferably 100 DEG C.Different temperatures is to reaction time and system
The quality of product have an impact.Anakmetomeres number increases in the rise of temperature, reaction solution, and effective collision increase, reaction rate adds
It hurry up, so that cause the generation of more gardenia blue pigments, but when temperature is too high, prolonged high temperature can be to gardenia blue pigment
Structure damage, the reduction of product color value on the contrary, it is therefore necessary to optimized to reaction temperature condition.
Step 1) described in amino acid and Geniposide mass ratio be 2:1.The different obtained gardenia blue pigments of mass ratio
Color value it is different.The mass ratio of reactant is too low, reaction can be caused incomplete, the product quality prepared is relatively low, mass ratio
It is too high, wastage of material can be caused.
In addition, by experiment, when the reaction time is 20min, just reaction is completed, and saves time and the energy.
Described amino acid calculates color value using following methods, and its step includes：
(1) concentration step 2) obtained gardenia blue pigment solution and it is dried in vacuo, obtain solid-state gardenia blue pigment powder；
(2) the solid-state gardenia blue pigment powder obtained using step (1) configures 0.1mg/mL gardenia blue pigment solution, and
Contrasted with standard color comparison card, qualitatively judge its colour generation；
(3) the gardenia blue pigment solution for preparing step (2) is in scanning ultraviolet spectra under 500~700nm, and calculates color
Valency,
Color value is calculated as follows：
Wherein：E is color value value；A is solution in the absorbance 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 synthesized by the gardenia blue pigment that microwave process for synthesizing is synthesized with respect to water bath heating
Its absorbance of pigment, which is substantially all, improves 10% or so.Show that its color value is higher, colorability is stronger.This be probably because
Microwave synthesis temperature is uniform, the same outside and inside, what the advantages of being quick on the draw was caused.Simultaneously relative to traditional heating water bath synthetic method
24h is needed to complete the synthesis of gardenia blue pigment, microwave process for synthesizing only needs 15min just can complete reaction, and this is substantially reduced
The time required to synthesis, energy consumption is reduced, combined coefficient is improved.
Compared with prior art, the present invention has the advantages that：
1st, gardenia blue pigment combined coefficient is greatly improved.Need 24h complete relative to traditional heating water bath synthetic method
Into the synthesis of gardenia blue pigment, microwave process for synthesizing is most fast only to need 15min just can complete reaction, and this substantially reduces synthesis and taken
Between, energy consumption is reduced, combined coefficient is improved.
2nd, product color value is high.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 with respect to water bath heating
Its absorbance 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.
Brief description of the drawings
Fig. 1 is each gardenia blue pigment solution of example three in maximum absorption wave strong point absorbance curve map；
Fig. 2 is each gardenia blue pigment solution of example four in maximum absorption wave strong point absorbance curve map；
Fig. 3 is each gardenia blue pigment solution of example five in maximum absorption wave strong point absorbance curve map；
Embodiment
The present invention is described in further detail with reference to specific embodiment.
Raw material used and equipment are as shown in table 1 in the examples below：
The raw material of table 1 and equipment source table
| Raw material or equipment | Supplier |
| Alanine | Beijing Suo Laibao Co., Ltds |
| Glycine | Beijing Chuan Xiu Science and Technology Ltd.s |
| Arginine | Shanghai Aladdin biochemical technology limited company |
| Lysine | Beijing North dawn membrane separation technique company |
| Histidine | Shanghai Shen An apparatuses factory |
| Microwave synthesizer | Pei An companies of the U.S. |
| Digital display thermostat water bath | High honour instrument manufacturing Co., Ltd of Jintan City |
| Dual-beam ultraviolet-uisible spectrophotometer | Beijing Pu Xi all purpose instruments Co., Ltd |
Embodiment one
Microwave is synthesized：Measure 5 parts of the genipin solution that 2mL concentration is 2mg/mL to be separately added into microwave reaction pipe, respectively
Measuring alanine, glycine, arginine, lysine, the histidine solution that 4mL concentration is 2mg/mL, to be separately added into above-mentioned microwave anti-
Ying Guan, setting power 150W, microwave synthesis 15min at 80 DEG C, obtain 5 parts of gardenia blue pigment solution.
Heating water bath is synthesized：Measure 5 parts of the genipin solution that 2mL concentration is 2mg/mL and be separately added into 5 20mL conical flasks
In, then measure alanine, glycine, arginine, lysine, histidine solution that 4mL concentration is 2mg/mL and be separately added into
Conical flask is stated, 80 DEG C of water-baths shake 24h, obtain 5 parts of gardenia blue pigment solution.
Detection and calculating：By microwave synthesize the gardenia blue pigment solution that is synthesized with heating water bath respectively dilute 10 times after
500~700nm scans ultraviolet spectra, and its result is as shown in table 2：
The comparison of 2 two kinds of synthetic methods of table
It can be seen from upper table, for same monoamino-acid as synthetic material, from different synthetic methods, its synthesis is obtained
The maximum absorption wavelength position of gardenia blue pigment be identical, show that two methods are suitable for the synthesis of gardenia blue pigment,
But the absorbance of the gardenia blue pigment synthesized by microwave process for synthesizing is substantially higher in the Cape jasmine synthesized by water bath heating
Sub- cyanine, its temperature is uniform when this is probably because of microwave synthesis, the same outside and inside, what the advantages of being quick on the draw was caused.Simultaneously
24h is needed to complete the synthesis of gardenia blue pigment relative to traditional heating water bath synthetic method, microwave process for synthesizing only needs 15min
Just reaction can be completed, the time required to this substantially reduces synthesis, energy consumption is reduced, improves combined coefficient.Therefore microwave is selected
Synthetic method, which prepares gardenia blue pigment, has preferable advantage.
Embodiment two
Measure 5 parts of the genipin solution that 2mL concentration is 2mg/mL to be separately added into microwave reaction pipe, then measure 4mL dense
Spend the alanine for 2mg/mL, glycine, arginine, lysine, histidine solution and be separately added into above-mentioned microwave reaction pipe, set
Power 150W, microwave synthesis 15min at 80 DEG C.The gardenia blue pigment prepared after microwave is synthesized through different aminoacids and Geniposide
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, each pigment solution colour is observed
Situation, and it is contrasted 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 the amino acid classes of table 3 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 suction of the gardenia blue pigment prepared with Geniposide
Receive peak position not necessarily consistent, but it is general all can be in the range of 585~610nm, and gardenia blue pigment absorption maximum
Peak position is more moved to long wave length direction, shows that its quality is better, color and luster is distincter, and colour generation is closer to beautiful blueness, therefore
Typically it is considered that the gardenia blue pigment that absorption peak is more 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 been 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 blueness
The standard of element.Therefore in order to ensure prepare 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, gardenia blue pigment color value prepared by lysine, glycine, alanine and Geniposide is higher, still
Its absorption maximum peak position does not meet the standard of qualified gardenia blue pigment with colour generation, and histidine reacts what is prepared with Geniposide
Although gardenia blue pigment meets standard, but its color value only 57.4, and colorability is poor, therefore they are not preferable gardenia blues
Pigment synthesis raw material.The gardenia blue pigment color value that arginine is prepared with Geniposide has reached 83.8, with stronger colorability,
And it also complies with the standard of 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
Measure 5 parts of the genipin solution that 2mL concentration is 2mg/mL to be separately added into microwave reaction pipe, then be separately added into 4mL
Concentration be 2mg/mL arginine solution, synthesis temperature be 80 DEG C, set respectively the reaction time as 5min, 10min, 15min,
20min, 25min, then extract reaction solution 10 times of maximum absorption wave strong point measurement absorbances of dilution, and its result is as shown in Figure 1.
As shown in Figure 1, within 5~20min periods, the increase of generated time at any time, the absorbance of reaction solution is gradually
Rise, analysis reason is probably because the increase of generated time at any time, more arginine polymerize with Geniposide obtains gardenia blue
Pigment, therefore the absorbance of reaction solution can gradually increase.But after the microwave time 20min is higher than, the absorbance of reaction solution
Value occurs in that situation about reducing by a small margin, and this is probably that the structure of gardenia blue pigment is damaged because of prolonged high temperature,
So as to result in the reduction of the absorbance of reaction solution.In summary, the generated time of microwave synthesis gardenia blue pigment should be selected
20min。
Example IV
Measure 5 parts of the genipin solution that 2mL concentration is 2mg/mL to be separately added into microwave reaction pipe, then be separately added into 4mL
Concentration is 2mg/mL arginine solution, reacts 20min in the case where temperature is 40 DEG C, 60 DEG C, 80 DEG C, 100 DEG C, 120 DEG C respectively, with
After extract reaction solution dilution 10 times of maximum absorption wave strong points measurement absorbances, its result is as shown in Figure 2.
As shown in Figure 2, there is the situation of reduction after first increasing in being gradually increasing with temperature, reaction solution absorbance, its
In reach highest at 100 DEG C, up to 0.882.This is probably because just having started to activate in the rise with temperature, reaction solution
Molecular number increases, effective collision increase, and reaction rate is accelerated, so that cause the synthesis of more gardenia blue pigments, therefore reaction
The absorbance of liquid can gradually increase, but when temperature is too high, prolonged high temperature can be caused to the structure of gardenia blue pigment
Destruction, has instead resulted in the reduction of reaction solution absorbance.Therefore the synthesis temperature of microwave synthesis gardenia blue pigment should select 100
℃。
Embodiment five
5 parts of the genipin solution that 2mL concentration is 2mg/mL is measured respectively to be separately added into microwave reaction pipe, then is separately added into
4mL concentration is 1mg/mL, 2mg/mL, 3mg/mL, 4mg/mL, 5mg/mL arginine solution, under conditions of temperature is 100 DEG C
20min is reacted, 10 times of maximum absorption wave strong point measurement absorbances of dilution, its concrete outcome such as Fig. 3 institutes 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, which is occurred in that, first increases situation about reducing afterwards, when both mass ratioes reach 2:Maximum is reached when 1, up to 0.879, is
Make the color value of obtained gardenia blue pigment 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 the implementation to the present invention
The restriction of mode.For those of ordinary skill in the field, other can also be made not on the basis of the above description
With the change and variation of form.Here all embodiments can not be exhaustive.It is every to belong to technical scheme
Row of the obvious changes or variations amplified out still in protection scope of the present invention.
Claims (10)
1. a kind of method for synthesizing gardenia blue pigment, it is characterised in that first mix genipin solution with Freamine Ⅲ, then
The setting of reaction time, reaction temperature and microwave power is completed by microwave synthesizer, cape jasmine is can obtain after the completion of reaction
Cyanine solution.
2. the method for synthesis gardenia blue pigment according to claim 1, it is characterised in that comprise the following steps：
1) genipin solution and Freamine Ⅲ are first mixed into reaction stoste, the wherein mass ratio of Geniposide and amino acid is 2：
1~5；
2) the reaction stoste and then by step 1) obtained is placed in microwave synthesizer, setting reaction temperature, microwave power, during reaction
Between 5~25min, that is, obtain gardenia blue pigment solution.
3. the method for synthesis gardenia blue pigment according to claim 2, it is characterised in that also including step 3)：By step
2) the gardenia blue pigment solution obtained dilutes 10 times, then scans ultraviolet spectra in 500~700nm.
4. the method for synthesis gardenia blue pigment according to claim 2, it is characterised in that step 2) described in microwave
Power is 150W.
5. the method for synthesis gardenia blue pigment according to claim 1 or 2, it is characterised in that described Freamine Ⅲ
For alanine, glycine, arginine, lysine or histidine solution.
6. it is according to claim 2 synthesis gardenia blue pigment method, it is characterised in that step 2) described in setting temperature
Spend for 40~120 DEG C, the reaction time is 20min.
7. it is according to claim 2 synthesis gardenia blue pigment method, it is characterised in that step 1) described in amino acid
It is 2 with Geniposide mass ratio：1.
8. the method for synthesis gardenia blue pigment according to claim 5, it is characterised in that described Freamine Ⅲ is essence
Propylhomoserin solution.
9. it is according to claim 6 synthesis gardenia blue pigment method, it is characterised in that step 2) described in setting temperature
Spend for 100 DEG C.
10. it is according to claim 2 synthesis gardenia blue pigment method, it is characterised in that described amino acid use with
Lower method calculates color value, and its step includes：
(1) concentration step 2) obtained gardenia blue pigment solution and it is dried in vacuo, obtain solid-state gardenia blue pigment powder；
(2) configure 0.1mg/mL gardenia blue pigment solution using step (1) obtained solid-state gardenia blue pigment powder, and with mark
Quasi- colorimetric card is contrasted, and qualitatively judges its colour generation；
(3) the gardenia blue pigment solution for preparing step (2) is in scanning ultraviolet spectra under 500~700nm, and calculates color value,
Color value is calculated as follows：
Wherein：E is color value value；A is solution in the absorbance of maximum absorption wave strong point；M is sample quality；F is extension rate,
When undiluted, f=1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107604696A (en) * | 2017-08-09 | 2018-01-19 | 天津工业大学 | A kind of gardenia blue pigment colouring method of wool fabric |
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| CN102304189A (en) * | 2011-07-20 | 2012-01-04 | 中国农业科学院农产品加工研究所 | Method for extracting anti-oxidant mung bean polysaccharide |
| CN102321144A (en) * | 2011-07-25 | 2012-01-18 | 陕西理工学院 | Method for extracting ursolic acid from red jujube |
| CN103614431A (en) * | 2013-12-02 | 2014-03-05 | 南京工业大学 | Method for preparing gardenia blue pigment by phase transfer catalysis |
| CN104099373A (en) * | 2014-07-24 | 2014-10-15 | 武汉绿孚生物工程有限责任公司 | Method for producing gardenia blue pigment |
| CN105624198A (en) * | 2016-03-10 | 2016-06-01 | 河南中大恒源生物科技股份有限公司 | Process for preparing high-purity gardenia blue pigment in different hues |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102304189A (en) * | 2011-07-20 | 2012-01-04 | 中国农业科学院农产品加工研究所 | Method for extracting anti-oxidant mung bean polysaccharide |
| CN102321144A (en) * | 2011-07-25 | 2012-01-18 | 陕西理工学院 | Method for extracting ursolic acid from red jujube |
| CN103614431A (en) * | 2013-12-02 | 2014-03-05 | 南京工业大学 | Method for preparing gardenia blue pigment by phase transfer catalysis |
| CN104099373A (en) * | 2014-07-24 | 2014-10-15 | 武汉绿孚生物工程有限责任公司 | Method for producing gardenia blue pigment |
| CN105624198A (en) * | 2016-03-10 | 2016-06-01 | 河南中大恒源生物科技股份有限公司 | Process for preparing high-purity gardenia blue pigment in different hues |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107604696A (en) * | 2017-08-09 | 2018-01-19 | 天津工业大学 | A kind of gardenia blue pigment colouring method of wool fabric |
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