CN109181352A - A method of black sesame melanin is modified to water-soluble black element - Google Patents
A method of black sesame melanin is modified to water-soluble black element Download PDFInfo
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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
- C09B61/00—Dyes of natural origin prepared from natural sources, e.g. vegetable sources
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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
- C09B68/00—Organic pigments surface-modified by grafting, e.g. by establishing covalent or complex bonds, in order to improve the pigment properties, e.g. dispersibility or rheology
- C09B68/40—Organic pigments surface-modified by grafting, e.g. by establishing covalent or complex bonds, in order to improve the pigment properties, e.g. dispersibility or rheology characterised by the chemical nature of the attached groups
- C09B68/42—Ionic groups, e.g. free acid
- C09B68/425—Anionic groups
- C09B68/4257—Carboxylic acid groups
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Abstract
The present invention relates to melanin solubility method of modifying fields.A method of black sesame melanin is modified to water-soluble black element, modification reaction is carried out under inert atmosphere nitrogen after amino acid, water, black sesame melanin are mixed, then it separates, obtain water-soluble black element, wherein, quality, the quality of amino acid, the volume ratio of water of black sesame melanin are 1g:(0.5-3) g:(50-80) mL, the amino acid is one of L-arginine, DL- arginine or DL-histidine.The present invention overcomes black sesame melanins not to be suitable for preparing the problem of oral preparation and food colour additive, coloring agent, medicine, health care product etc. because not soluble in water.
Description
Technical field
The present invention relates to melanin solubility method of modifying field, it is especially a kind of black sesame melanin is modified to it is water-soluble
The method of property melanin.
Background technique
Melanin (Melanin) is prevalent in living nature, is to be currently known the wide color in source in biochrome
One of element is a kind of structure is complicated the phenols of multiplicity or general name of indoles large biological molecule pigment.According to the difference in structure,
Eumelanin (eumelanins), pheomelanins (phaeomelanins) and allpmelanin (allomelanins) can be divided into
Three types.Melanin has many unique functional characteristics, not only serve as a kind of bright protective agent, anti-rad, chelating agent,
Biological anti-oxidant and immunopotentiating agent, and it is alternatively arranged as a kind of biological semiconductor materials.Research in recent years also found, black
Pigment has the effects that anti-snake venom, anticancer, inhibits AIDS virus duplication, treatment parkinsonism, in medicine, cosmetics, food, electricity
The fields such as son have a wide range of applications.
But melanin is not soluble in water mostly and most organic solvent, is only soluble in alkaline solution, precipitates in an acidic solution,
These special natures cause it to be restricted in the application in the fields such as food, medical treatment.Alkali solubility melanin is modified into water solubility
Melanin gives full play to its biological function convenient for its exploitation and application, application field and applicable model for extension melanin
It encloses with positive effect.Currently, the market of melanin is mainly based on chemical synthesis.
Summary of the invention
The technical problems to be solved by the present invention are: how to solve the deficiencies in the prior art, provide it is a kind of will be black
The method that sesame melanin is modified to water-soluble black element.
The technical scheme adopted by the invention is that: a method of black sesame melanin is modified to water-soluble black element,
Modification reaction is carried out under inert atmosphere nitrogen after amino acid, water, black sesame melanin are mixed, and is then separated, is obtained water-soluble
Property melanin, wherein the quality of black sesame melanin, the quality of amino acid, the volume ratio of water are 1g:(0.5-3) g:(50-80)
ML, the amino acid are one of L-arginine, DL- arginine or DL-histidine.
As a kind of preferred embodiment: the condition of the modification reaction is to carry out under inert atmosphere stirred under nitrogen, stirring
Speed is 200-800rpm, and time 5-20min, temperature is 25-37 DEG C.
As a kind of preferred embodiment: the isolated process is that modified outcome is carried out centrifugal treating, obtains supernatant,
Wherein, the condition of the centrifugal treating are as follows: revolving speed: 8000-12000r/min, time: 5-10min；Supernatant is dialysed
It is freeze-dried after processing, wherein the condition of dialysis treatment is that the molecule interception of bag filter is 1000-2000D, dialysis
Time is 36-48h, and the condition of freeze-drying is that temperature is subzero 40 DEG C to subzero 45 DEG C, pressure 5-13Pa.
As a kind of preferred embodiment: the preparation step position of the black sesame melanin:
A, it is ultrasonically treated after mixing Semen sesami nigrum with lye, obtains the first mixed liquor；
B, the first mixed liquor obtained by step a is filtered, obtains filtrate product；
C, centrifugal treating is carried out after filtrate product obtained by step b being adjusted pH value to 1.0-3.0 using acid solution, centrifugation gained is heavy
It forms sediment and carries out vacuum freeze drying, obtain black sesame melanin crude product；
D, black sesame melanin crude product obtained by step c is dissolved in after lye and use acid solution adjusting pH for 1.0-3.0, then carry out from
Heart processing, obtains single treatment black sesame melanin crude product；
E, single treatment black sesame melanin crude product obtained by step d is subjected to acidolysis processing using acid solution, is then centrifuged for obtaining two
Secondary processing black sesame melanin crude product；
F, secondary treatment black sesame melanin crude product obtained by step e is washed and is centrifuged using organic solvent, obtained three times
Handle black sesame melanin crude product；
It g, will to obtain required Semen sesami nigrum black for vacuum freeze drying after processing black sesame melanin is washed three times obtained by step f
Pigment sterling.
As a kind of preferred embodiment: in step a, the lye be 1-3mol/L NaOH solution, the quality of Semen sesami nigrum with
The ratio of lye volume is 1g:(1-5) mL, the condition of ultrasonic treatment is frequency 40-60Hz, time 40-180min；
The mode filtered in step b is to filter；
Acid solution described in step c is 2-8mol/L hydrochloric acid, and the revolving speed of centrifugal treating is 8000-12000r/min, centrifugal treating
Time is 5-10min, the condition of vacuum freeze drying are as follows: temperature is subzero 60 DEG C to subzero 80 DEG C, pressure 4-15Pa；
Lye described in step d is 1-3mol/L NaOH solution, the ratio of the volume of the quality and lye of black sesame melanin crude product
Example is 1g:(1-5) mL, acid solution is 2-8mol/L hydrochloric acid, and the revolving speed of centrifugal treating is 8000-12000r/min, centrifugal treating
Time is 5-10min；
Acid solution described in step e is 2-8mol/L hydrochloric acid, the quality of single treatment black sesame melanin crude product and the volume of acid solution
Ratio be 1g:(1-5) mL, acidolysis processing condition be, temperature be 90-100 DEG C, time 60-180min；
It is successively washed using chloroform, ethyl acetate and ethyl alcohol in step f, the quality of secondary treatment black sesame melanin crude product
Ratio with the volume of every kind of organic solvent is 1g:(5-40) mL, the condition of centrifugation are as follows: revolving speed 8000-12000r/min, when
Between be 5-10min；
Vacuum drying condition is in step g, and temperature is subzero 60 DEG C to subzero 80 DEG C, pressure 4-15Pa.
The beneficial effects of the present invention are: black sesame melanin effectively can be modified to water-soluble black element by the present invention,
To overcome black sesame melanin not to be suitable for preparing oral preparation and food colour additive, dyeing because not soluble in water
The problem of agent, medicine, health care product etc., the application range for expanding black sesame melanin have positive meaning.
Detailed description of the invention
Fig. 1 is modification effect figure of the variety classes amino acid to black sesame melanin；
Fig. 2 is the mass ratio of black sesame melanin and L-arginine and the corresponding relationship curve graph of modification rate；
Fig. 3 is the corresponding relationship curve graph of black sesame melanin and the arginic mass ratio of DL- and modification rate；
Fig. 4 is the mass ratio of black sesame melanin and DL-histidine and the corresponding relationship curve graph of modification rate；
Fig. 5 is the infrared spectrum of black sesame melanin；
Fig. 6 is L-arginine/melanin infrared spectrum；
Fig. 7 is DL- arginine/melanin infrared spectrum；
Fig. 8 is DL-histidine/melanin infrared spectrum.
Specific embodiment
The invention will be further described combined with specific embodiments below, and following embodiment and explanation are used to explain this hair
It is bright but not as a limitation of the invention.
It is reacted under inert atmosphere nitrogen after amino acid, water and black sesame melanin are mixed, is then separated, obtained
To water-soluble black element.Wherein, the volume ratio of the quality of black sesame melanin, the quality of amino acid and water is 1g:(0.5-3) g:
(50-80) mL, the amino acid are L-arginine, DL- arginine or DL-histidine.
Semen sesami nigrum 30g is weighed, the preferred 2mol/L of 1-3mol/L(is dissolved in) in NaOH solution, the quality and NaOH of Semen sesami nigrum are molten
The volume ratio of liquid is 1g:(1-5) the preferred 1g:3mL of mL(), ultrasound condition is excellent for the preferred 60Hz of 40-60Hz(), 200-400W(
Select 200W), the preferred 120min of extraction time 40-180min(), obtain the first mixed liquor.
First mixed liquor is filtered and obtains filtrate product.
Gained filtrate product is carried out to carry out centrifugal treating after acid solution adjusts pH value, gained is precipitated into progress vacuum refrigeration and is done
Dry, obtaining freeze-drying product is black sesame melanin crude product.The acid solution is the preferred 6mol/L of 2-8mol/L() hydrochloric acid solution,
Preferably 2.0) adjusted pH, is stood to melanin deposition for 1.0-3.0(, excellent using supercentrifuge 8000-12000r/min(
Select 9000r/min), centrifugation the preferred 5min of 5-10min() removal supernatant, must precipitate.Using vacuum freeze drier, -60
DEG C~-80 DEG C, under 4-15Pa pressure condition after vacuum freeze drying to get black sesame melanin crude product, can be black by what is obtained
Sesame melanin crude product saves at 4 DEG C.
Black sesame melanin crude product is dissolved in after lye, pH is adjusted using acid solution, then carries out centrifugal treating, Semen sesami nigrum is black
The ratio of the volume of the quality and lye of pigment crude product is 1g:(1-5) the preferred 1g:2mL of mL(), the lye is 1-3 mol/L
(preferably 2 mol/L) NaOH solution, that is, the crude product of black sesame melanin is dissolved in again in 1-3 mol/L NaOH solution, acid
Liquid be the preferred 6mol/L of 2-8mol/L() hydrochloric acid, with 2-8mol/L hydrochloric acid solution adjust pH value to 1.0-3.0(preferably 2.0),
8000-12000r/min is centrifuged (preferably 9000r/min), is centrifuged the preferred 5min of 5-10min() supernatant is removed, solid is collected,
The step is repeated 3 times above (preferably 3 times), obtains single treatment black sesame melanin crude product.
Single treatment black sesame melanin crude product is subjected to acidolysis processing using acid solution, then washes and is centrifuged, obtain two
Secondary processing black sesame melanin crude product.Wherein, the acid solution is the preferred 6mol/L of 2-8mol/L() HCl solution, and single treatment is black
The ratio of the volume of the quality and acid solution of sesame melanin crude product is 1g:(1-5) the preferred 1g:3mL of mL(), it is heated to 90-100 DEG C
The preferred 90min of acidolysis 60-180min(in (preferably 100 DEG C) water-bath) to remove the impurity such as protein, carbohydrate and lipid,
Remove hydrochloric acid, centrifugation washing melanin deposition, until not containing Cl in detection water lotion-。
Secondary treatment black sesame melanin crude product is washed and is centrifuged using organic solvent, is handled black sesame three times
Dark pigment crude product.Successively washed using chloroform, ethyl acetate and ethyl alcohol, which is repeated 3 times above (preferably 3 times),
The ratio of the volume of the quality and every kind of organic solvent of secondary treatment black sesame melanin crude product is 1g:(5-40) the preferred 1g of mL(:
10mL), the condition of centrifugation are as follows: revolving speed is the preferred 9000r/min of 8000-12000r/min(), the time is that 5-10min(is preferred
5min).
By the quality of secondary treatment black sesame melanin crude product and the volume of chloroform, proportionally 1g:10mL is sufficiently shaken up,
Supernatant is removed with the revolving speed centrifugation 5min of 9000r/min, solid is collected, repeats the step 3 time, until supernatant is colourless；Again
By the quality for the solid that previous step obtains and the volume of ethyl acetate, proportionally 1g:10mL is sufficiently shaken up, with 9000r/min
Revolving speed centrifugation 5min remove supernatant, collect solid, repeat the step 3 time, until supernatant be it is colourless；Finally by previous step
Proportionally 1g:10mL sufficiently shakes up for the quality of obtained solid and the volume of dehydrated alcohol, is centrifuged with the revolving speed of 9000r/min
5-10min removes supernatant, collects solid, as handles black sesame melanin crude product three times, the step 3 time is repeated, until supernatant
Liquid is colourless.
Vacuum freeze drying after black sesame melanin crude product is washed will be handled three times, obtain required Semen sesami nigrum black
Plain sterling.It can repeatedly be washed, with vacuum freeze drier vacuum refrigeration under -60~-80 DEG C, 4-15Pa pressure condition
To get the higher black sesame melanin of purity after drying, can be saved at 4 DEG C.It is higher that purity is prepared by above step
Black sesame melanin.In the modification of next black sesame melanin, the matter of black sesame melanin and L-arginine
Measuring ratio can be 1:(0.5-3)；Black sesame melanin and the arginic mass ratio of DL- can be 1:(0.5-3)；Semen sesami nigrum black
Element and the mass ratio of DL-histidine can be 1:(0.5-3).
The condition of the modification is to carry out under stiring in inert nitrogen gas, mixing speed 200-800rpm, the time
For 5-20min, temperature is 25-37 DEG C.
The step of separation is that modified outcome carries out centrifugal treating, obtains supernatant, wherein the centrifugal treating
Condition are as follows: revolving speed 8000-12000r/min, time 5-10min；It is freezed after the supernatant is carried out dialysis treatment
It is dry, wherein the condition of the dialysis treatment includes: that the molecule interception of bag filter is 1000-2000D, dialysis time 36-
48h, the condition of the freeze-drying include: that temperature is subzero 40 DEG C to subzero 45 DEG C, pressure 5-13Pa.
Through the above technical solutions, water-soluble black element effectively can be modified to black sesame melanin, to overcome
Black sesame melanin is not suitable for preparing oral preparation and food colour additive, coloring agent, medicine, guarantor because not soluble in water
The problem of strong product etc., the application range for expanding black sesame melanin have positive meaning.
Embodiment 1
In the present embodiment: taking L-arginine 0.9g that 30mL distilled water is added and dissolved, then accurately weigh black sesame melanin
0.6g is fed intake respectively in tri- mouthfuls of reactors of 100mL, connects condenser pipe and mechanical stirring device, temperature is 25 DEG C, in indifferent gas
Under body nitrogen atmosphere, with the revolving speed mechanical stirring of 200rpm, taking-up after 5min is mixed, 5min is centrifuged using 11000r/min,
Collect supernatant.Then it is taken out after supernatant being put into the bag filter that molecule interception is 1000D the 48h that dialyses, it is cold with vacuum
Lyophilizer dries finished product under -40~-45 DEG C, 5 ~ 13Pa pressure condition to get solid articles water solubility Semen sesami nigrum black is arrived
Element.
Embodiment 2
In the present embodiment: taking DL- arginine 0.8g that 48mL distilled water is added and dissolved, then accurately weigh black sesame melanin
0.4g is fed intake respectively in tri- mouthfuls of reactors of 100mL, connection condenser pipe and mechanical stirring device, and 25 DEG C of temperature, in inert gas
It is taken out after 200rpm mechanical stirring mixing 5min under nitrogen atmosphere, 5min is centrifuged using 11000r/min, collects supernatant, so
It is taken out after supernatant is put into the bag filter that molecule interception is 1000D the 48h that dialyses afterwards, with vacuum freeze drier -40
~-45 DEG C, under 5 ~ 13Pa pressure condition dry finished product to get arriving solid articles water solubility black sesame melanin.
Embodiment 3
In the present embodiment: taking DL-histidine 1g that 80mL distilled water is added and dissolved, then accurately weigh black sesame melanin
0.4g is fed intake respectively in tri- mouthfuls of reactors of 100mL, connection condenser pipe and mechanical stirring device, and 25 DEG C of temperature, in inert gas
It is taken out after 200rpm mechanical stirring mixing 6min under nitrogen atmosphere, 5min is centrifuged using 11000r/min, collects supernatant.So
It is taken out after supernatant is put into the bag filter that molecule interception is 1000D the 48h that dialyses afterwards, with vacuum freeze drier -40
~-45 DEG C, under 5 ~ 13Pa pressure condition dry finished product to get arriving solid articles water solubility black sesame melanin.
Comparative experiments example
Water-soluble black element preparation process: take L-arginine, DL- arginine, DL-histidine, L-Methionine, altheine each
0.5g is separately added into 40mL distilled water and carries out dissolution 5 parts of mixtures of generation, in addition prepares portion 40mL distilled water and is used as control not
Amino acid is added, thus generates 6 parts, is fed intake in 6 100mL, tri- mouthfuls of reactors respectively.It is black that 6 portions of Semen sesami nigrums are accurately weighed again
Pigment, every part of 0.5g are fed intake respectively in above-mentioned 6 100mL, tri- mouthfuls of reactors, connect condenser pipe and mechanical stirring device,
500rpm mechanical stirring mixing 8min under inert nitrogen gas atmosphere, 30 DEG C of temperature.It takes out, is centrifuged using 10000r/min later
Supernatant is collected after 10min, surveys its OD after diluting identical multiple500Value, light absorption value is higher to show that solute effect is better.Fig. 1 is not
Modification effect figure of the amino acid of the same race to black sesame melanin.As shown in Figure 1, wherein with L-arginine, DL- arginine, DL-
The melanin absorbance of histidine modification is maximum, OD500Value is respectively 0.327,0.320,0.18；And with methionine, asparagine
The melanin OD of modification500Value is respectively 0.099,0.094, and modification effect is inferior to L-arginine, DL- arginine and DL- group
Propylhomoserin modifies melanin.
To obtain black sesame melanin modifier finished product, the supernatant obtained after being centrifuged in above-mentioned steps is put into 1000D
Bag filter in dialyse 48h after take out, with vacuum freeze drier, vacuum is cold under -40 DEG C~-45 DEG C, 5 ~ 13Pa pressure condition
Be lyophilized it is dry after to get to solid articles water solubility black sesame melanin.To obtained solid articles water solubility black sesame melanin
Carry out solubility experiment, the results showed that L-arginine/melanin, DL- arginine/melanin, DL-histidine/melanin are water-soluble
Property effect effect more water-soluble than L-Methionine/melanin, altheine/melanin is more preferable.
The mass ratio of black sesame melanin is modified in order to further determine L-arginine, DL- arginine and DL-histidine,
It is tested below, specific as follows:
Verify example 1
L-arginine 0.15,0.3,0.45,0.6,0.75,0.9g is taken to be separately added into 6 parts of 50mL distilled water and dissolved, then accurately
6 parts of black sesame melanins are weighed, every part of 0.3g, feed intake in tri- mouthfuls of reactors of 100mL (black sesame melanin and L- essence ammonia respectively
The mass ratio of acid is 1:0.5,1:1,1:1.5,1:2,1:2.5,1:3), subsequent experimental procedure is with embodiment 1, by obtain 6 parts
Solid articles water solubility black sesame melanin surveys its OD after diluting identical multiple500Value.Fig. 2 is what an exemplary embodiment provided
The corresponding relationship curve graph of the mass ratio and modification rate of black sesame melanin and L-arginine.As shown in Fig. 2, when L-arginine adds
It is modified melanin meltage and increases when entering amount increase, and when mass ratio is 1:2.5, modification melanin can be completely dissolved,
OD500Value is 0.600, reaches maximum, continues to increase L-arginine amount, then OD500Value is not further added by, and is reduced instead.As it can be seen that black sesame
The mass ratio of dark pigment and L-arginine is that 1:2.5 is preferable.
Verify example 2
DL- arginine 0.15,0.3,0.45,0.6,0.75,0.9g is taken to be separately added into 6 parts of 50mL distilled water and dissolved, then quasi-
6 parts of black sesame melanins really are weighed, every part of 0.3g, feed intake (black sesame melanin and DL- in tri- mouthfuls of reactors of 100mL respectively
Arginic mass ratio is 1:0.5,1:1,1:1.5,1:2,1:2.5,1:3), subsequent experimental procedure is with embodiment 1, by what is obtained
6 parts of solid articles water solubility black sesame melanins survey its OD after diluting identical multiple500Value.Fig. 3 provides for an exemplary embodiment
Black sesame melanin and the arginic mass ratio of DL- and modification rate corresponding relationship curve graph.As shown in figure 3, working as DL- essence ammonia
It is modified melanin meltage and increases when sour additional amount increases, and when mass ratio is 1:2, modification melanin can be completely molten
Solution, OD500Value is 0.539, reaches maximum, continues to increase DL- arginine amount, then OD500Value is not further added by, and is reduced instead.As it can be seen that
Black sesame melanin is that 1:2 is preferable with the arginic mass ratio of DL-.
Verify example 3
DL-histidine 0.15,0.3,0.45,0.6,0.75,0.9g is taken to be separately added into 6 parts of 50mL distilled water and dissolved, then quasi-
6 parts of black sesame melanins really are weighed, every part of 0.3g, feed intake (black sesame melanin and DL- in tri- mouthfuls of reactors of 100mL respectively
The mass ratio of histidine is 1:0.5,1:1,1:1.5,1:2,1:2.5,1:3), subsequent experimental procedure is with embodiment 1, by what is obtained
6 parts of solid articles water solubility black sesame melanins survey its OD after diluting identical multiple500Value.Fig. 4 provides for an exemplary embodiment
Black sesame melanin and DL-histidine mass ratio and modification rate corresponding relationship curve graph.As shown in figure 4, working as DL- group ammonia
When sour additional amount increases, modification melanin meltage increases, and when mass ratio is 1:1.5, melanin can be completely dissolved,
OD500Value is 0.446, reaches maximum, continues to increase DL-histidine amount, then OD500Value is not further added by, and is reduced instead.As it can be seen that black
Sesame melanin and the mass ratio of DL-histidine are that 1:1.5 is preferable.
The measurement of solubility
The black sesame melanin of modification front and back is dissolved in respectively in different solution, dissolubility and solution colour are observed.Table 1 is shown
Black sesame melanin, L-arginine/melanin, DL- arginine/melanin and DL-histidine/melanin dissolubility knot
Fruit.Wherein, plus sige more multilist shows that solubility is higher, and minus sign more multilist shows that solubility is lower.As shown in table 1, black before unmodified
Sesame melanin is slightly soluble in water (+--), be only soluble in 1mol/LNaOH alkaline aqueous solution and dimethyl sulfoxide (DMSO) solution (++
+), (---) is precipitated in acid solution (1mol/L HCl).After amino acid modification, L-arginine/melanin, DL- essence ammonia
Acid/melanin, DL-histidine/melanin dissolve in distilled water (+++), all have preferable water solubility.Fig. 5 shows for one
Semen sesami nigrum-melanin, the L-arginine-melanin, DL-histidine-melanin dissolubility result figure that example property embodiment provides.
Table 1
The characterization of water-soluble black element
, with the 2mg black sesame melanin after modification, tabletting will be mixed with 400mg dry KBr respectively, using FT- before modification
IR6700 Fourier transformation infrared spectrometer is in 4000 ~ 400cm-1Section carries out infrared spectrum measurement.
Infrared spectroscopy can characterize the main function group in melanin structure.Fig. 5 provides for an exemplary embodiment
Black sesame melanin infrared spectrum.As shown in figure 5, black sesame melanin is as other natural black pigments, infrared light
Spectrum is a series of wide and strong absorption peak, shows complicated large biological molecule compound characteristic, and each broad peak is all
It is to be vibrated by a variety of functional groups superimposed as a result, lacking characteristic.The characteristic absorption of black sesame pigment mainly has: (1) existing
3408cm-1It is by-OH ,-NH there are stronger RESONANCE ABSORPTION2, while the region also belongs to the stretching vibration of-COOH.(2) exist
2940~absorb main 2900cm-1(2923cm nearby-1) there is relatively weak absorption peak, reflect that the C-H of alkane structure stretches
Contracting vibration.(3) in 1618 cm-1Left and right has aromatic ring frame vibration to cause stronger absorption peak, for the vibration of fragrant ring skeleton C=C
It absorbs, illustrates the presence for having phenyl ring in black sesame melanin molecular structure.(4) 1125~1000cm-1Locate (1075.62 cm-1)
Absorption peak, partially by C-CH3Curved and skeletal vibration absorb and participate in and formed.(5) in 865~660cm-1Absorption in range
It is weaker, it indicates that aromatic ring is substituted, forms conjugated system, fragrant hydrogen content is less.To sum up, the official that black sesame melanin may have
Can roll into a ball has :-OH ,-NH2、-COOH、C-H、C=C、C-CH3。
Fig. 6 is L-arginine/melanin infrared spectrum that an exemplary embodiment provides.Comparative analysis Fig. 5 and Fig. 6 can
To find out, the black sesame melanin of front and back is modified in addition to the universal characteristic absorption peak of most melanin, L-arginine/black
Element is in 3200 cm-1、1405.42 cm-1、1020 cm-1、622.87 cm-1There is the characteristic absorption peak of L-arginine at place；With black sesame
Dark pigment compares, in 1432.08 cm-1、1267.99 cm-1Locate L-arginine/black peak intensity to weaken, this may be
Since the vibration of group after L-arginine modification is changed.These the result shows that L-arginine to black sesame melanin have compared with
Good modified effect.
Fig. 7 is DL- arginine/melanin infrared spectrum that an exemplary embodiment provides.Comparative analysis Fig. 5 and Fig. 7
The black sesame melanin of modification front and back be can be seen that in addition to the universal characteristic absorption peak of most melanin, DL- arginine/
Melanin is in 1020 cm-1There is the arginic characteristic absorption peak of DL- at place；And compared with black sesame melanin, Semen sesami nigrum black
1432.08 cm of element-1.The peak at place moves right to 1404.05cm-1Place, 1269.67cm-1Locate peak intensity to weaken, 480cm-1Place
Peak disappears, it may be possible to since the vibration of group after the modification of DL- arginine is changed.These are the result shows that DL- arginine pair
Black sesame melanin has preferable modified to act on.
Fig. 8 is DL-histidine/melanin infrared spectrum that an exemplary embodiment provides, comparative analysis Fig. 5 and Fig. 8
The black sesame melanin of modification front and back be can be seen that in addition to the universal characteristic absorption peak of most melanin, DL-histidine/
Melanin is in 1020 cm-1、625.55 cm-1There is the characteristic absorption peak of DL-histidine at place；And compared with black sesame melanin
Compared with 1432.08 cm-1The peak at place moves right to 1405.14cm-1Place, it may be possible to due to the vibration of group after DL-histidine modification
It is dynamic to be changed.These are the result shows that DL-histidine has preferable modified to act on black sesame melanin.
Claims (5)
1. a kind of method that black sesame melanin is modified to water-soluble black element, it is characterised in that: by amino acid, water, black sesame
Modification reaction is carried out under inert atmosphere nitrogen after dark pigment mixing, is then separated, and obtains water-soluble black element, wherein black
The quality of sesame melanin, the quality of amino acid, the volume ratio of water are 1g:(0.5-3) g:(50-80) mL, the amino acid is
One of L-arginine, DL- arginine or DL-histidine.
2. the method according to claim 1 that black sesame melanin is modified to water-soluble black element, it is characterised in that: institute
The modification reaction condition stated is to carry out under stiring, mixing speed 200-800rpm, time 5-20min, temperature 25-
37℃。
3. the method according to claim 1 that black sesame melanin is modified to water-soluble black element, it is characterised in that: institute
The process for stating separation is that modified outcome is carried out centrifugal treating, obtains supernatant, wherein the condition of the centrifugal treating are as follows: is turned
Speed: 8000-12000r/min, time: 5-10min；It is freeze-dried after supernatant is carried out dialysis treatment, wherein dialysis
The condition of processing is that the molecule interception of bag filter is 1000-2000D, dialysis time 36-48h, the condition of freeze-drying
For temperature is subzero 40 DEG C to subzero 45 DEG C, pressure 5-13Pa.
4. the method according to claim 1 that black sesame melanin is modified to water-soluble black element, it is characterised in that: institute
State the preparation step of black sesame melanin are as follows:
A, it is ultrasonically treated after mixing Semen sesami nigrum with lye, obtains the first mixed liquor；
B, the first mixed liquor obtained by step a is filtered, obtains filtrate product；
C, centrifugal treating is carried out after filtrate product obtained by step b being adjusted pH value to 1.0-3.0 using acid solution, centrifugation gained is heavy
It forms sediment and carries out vacuum freeze drying, obtain black sesame melanin crude product；
D, black sesame melanin crude product obtained by step c is dissolved in after lye and use acid solution adjusting pH for 1.0-3.0, then carry out from
Heart processing, obtains single treatment black sesame melanin crude product；
E, single treatment black sesame melanin crude product obtained by step d is subjected to acidolysis processing using acid solution, is then centrifuged for, obtains two
Secondary processing black sesame melanin crude product；
F, secondary treatment black sesame melanin crude product obtained by step e is washed and is centrifuged using organic solvent, obtained three times
Handle black sesame melanin crude product；
It g, will to obtain required Semen sesami nigrum black for vacuum freeze drying after processing black sesame melanin is washed three times obtained by step f
Pigment sterling.
5. the method according to claim 4 that black sesame melanin is modified to water-soluble black element, it is characterised in that:
In step a, the lye is the NaOH solution of 1-3mol/L, and the quality of Semen sesami nigrum and the ratio of lye volume are 1g:(1-
5) condition of mL, ultrasonic treatment are frequency 40-60Hz, time 40-180min；
The mode filtered in step b is to filter；
Acid solution described in step c is 2-8mol/L hydrochloric acid, and the revolving speed of centrifugal treating is 8000-12000r/min, centrifugal treating
Time is 5-10min, and the condition of vacuum freeze drying is that temperature is subzero 60 DEG C to subzero 80 DEG C, pressure 4-15Pa；
Lye described in step d is 1-3mol/L NaOH solution, the ratio of the volume of the quality and lye of black sesame melanin crude product
Example is 1g:(1-5) mL, acid solution is 2-8mol/L hydrochloric acid, and revolving speed from processing is 8000-12000r/min, centrifugal treating when
Between be 5-10min；
Acid solution described in step e is 2-8mol/L hydrochloric acid, the quality of single treatment black sesame melanin crude product and the volume of acid solution
Ratio be 1g:(1-5) mL, acidolysis processing condition be, temperature be 90-100 DEG C, time 60-180min；
It is successively washed using chloroform, ethyl acetate and ethyl alcohol in step f, the quality of secondary treatment black sesame melanin crude product
Ratio with the volume of every kind of organic solvent is 1g:(5-40) mL, the condition of centrifugation are as follows: revolving speed 8000-12000r/min, when
Between be 5-10min；
Vacuum drying condition is in step g, and temperature is subzero 60 DEG C to subzero 80 DEG C, pressure 4-15Pa.
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| CN114316624B (en) * | 2021-12-13 | 2023-04-18 | 山西农业大学 | Method for performing amino acid modification on morchella ladder melanin |
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