CN106188261B - A kind of lemon acid albumin, its preparation method and its derived product - Google Patents
A kind of lemon acid albumin, its preparation method and its derived product Download PDFInfo
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- CN106188261B CN106188261B CN201610665908.3A CN201610665908A CN106188261B CN 106188261 B CN106188261 B CN 106188261B CN 201610665908 A CN201610665908 A CN 201610665908A CN 106188261 B CN106188261 B CN 106188261B
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- lemon acid
- protein
- albumin
- acid albumin
- citric
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- 239000002253 acid Substances 0.000 title claims abstract description 157
- 235000005979 Citrus limon Nutrition 0.000 title claims abstract description 146
- 102000009027 Albumins Human genes 0.000 title claims abstract description 133
- 108010088751 Albumins Proteins 0.000 title claims abstract description 133
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 244000248349 Citrus limon Species 0.000 title abstract 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 128
- 102000004169 proteins and genes Human genes 0.000 claims abstract description 48
- 108090000623 proteins and genes Proteins 0.000 claims abstract description 48
- WQNHWIYLCRZRLR-UHFFFAOYSA-N 2-(3-hydroxy-2,5-dioxooxolan-3-yl)acetic acid Chemical compound OC(=O)CC1(O)CC(=O)OC1=O WQNHWIYLCRZRLR-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000005917 acylation reaction Methods 0.000 claims abstract description 19
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims abstract description 4
- 244000131522 Citrus pyriformis Species 0.000 claims description 144
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 60
- 235000018102 proteins Nutrition 0.000 claims description 46
- 229910052742 iron Inorganic materials 0.000 claims description 30
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 claims description 22
- 235000021240 caseins Nutrition 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 15
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 14
- 239000011575 calcium Substances 0.000 claims description 14
- 229910052791 calcium Inorganic materials 0.000 claims description 14
- 230000010933 acylation Effects 0.000 claims description 13
- 108010073771 Soybean Proteins Proteins 0.000 claims description 12
- 235000019710 soybean protein Nutrition 0.000 claims description 12
- 239000005018 casein Substances 0.000 claims description 11
- 235000021120 animal protein Nutrition 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 3
- 244000105624 Arachis hypogaea Species 0.000 claims description 3
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 3
- 235000018262 Arachis monticola Nutrition 0.000 claims description 3
- 240000002900 Arthrospira platensis Species 0.000 claims description 3
- 235000016425 Arthrospira platensis Nutrition 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 102000008186 Collagen Human genes 0.000 claims description 3
- 108010035532 Collagen Proteins 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229920001436 collagen Polymers 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 235000020232 peanut Nutrition 0.000 claims description 3
- 239000011669 selenium Substances 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 229940082787 spirulina Drugs 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- 150000003141 primary amines Chemical group 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims 1
- 230000000536 complexating effect Effects 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 5
- 108091005647 acylated proteins Proteins 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 210000000936 intestine Anatomy 0.000 abstract description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 2
- 210000002784 stomach Anatomy 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 85
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 70
- 229960004106 citric acid Drugs 0.000 description 39
- 235000011121 sodium hydroxide Nutrition 0.000 description 34
- 239000000047 product Substances 0.000 description 33
- 238000001556 precipitation Methods 0.000 description 32
- 238000003756 stirring Methods 0.000 description 31
- 230000006920 protein precipitation Effects 0.000 description 27
- 102000011632 Caseins Human genes 0.000 description 20
- 108010076119 Caseins Proteins 0.000 description 20
- 239000003643 water by type Substances 0.000 description 19
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical group OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 18
- 238000005119 centrifugation Methods 0.000 description 16
- 239000012043 crude product Substances 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 229940021722 caseins Drugs 0.000 description 11
- RUWKZSPFMDVLRC-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;zinc Chemical compound [Zn].OC(=O)CC(O)(C(O)=O)CC(O)=O RUWKZSPFMDVLRC-UHFFFAOYSA-N 0.000 description 9
- 150000008064 anhydrides Chemical class 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 238000005070 sampling Methods 0.000 description 9
- QCVGEOXPDFCNHA-UHFFFAOYSA-N 5,5-dimethyl-2,4-dioxo-1,3-oxazolidine-3-carboxamide Chemical compound CC1(C)OC(=O)N(C(N)=O)C1=O QCVGEOXPDFCNHA-UHFFFAOYSA-N 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- 102000002322 Egg Proteins Human genes 0.000 description 8
- 108010000912 Egg Proteins Proteins 0.000 description 8
- 235000014103 egg white Nutrition 0.000 description 8
- 210000000969 egg white Anatomy 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 6
- 239000012460 protein solution Substances 0.000 description 6
- 239000011573 trace mineral Substances 0.000 description 6
- 235000013619 trace mineral Nutrition 0.000 description 6
- 108010084684 iron protein succinylate Proteins 0.000 description 5
- 229940074442 iron protein succinylate Drugs 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic acid anhydride Natural products CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 4
- 239000001110 calcium chloride Substances 0.000 description 4
- 229910001628 calcium chloride Inorganic materials 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 235000013601 eggs Nutrition 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 230000004060 metabolic process Effects 0.000 description 3
- 229940029985 mineral supplement Drugs 0.000 description 3
- 239000001384 succinic acid Substances 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- -1 Shi Hao Chemical class 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002496 gastric effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000002207 metabolite Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NJFMNPFATSYWHB-UHFFFAOYSA-N ac1l9hgr Chemical compound [Fe].[Fe] NJFMNPFATSYWHB-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical group 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229960004543 anhydrous citric acid Drugs 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001198 duodenum Anatomy 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000031891 intestinal absorption Effects 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000003257 protein preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K14/00—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof
- C07K14/435—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K14/00—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof
- C07K14/415—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from plants
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biophysics (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Gastroenterology & Hepatology (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Medicinal Chemistry (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Botany (AREA)
- Toxicology (AREA)
- Zoology (AREA)
- Coloring Foods And Improving Nutritive Qualities (AREA)
- Peptides Or Proteins (AREA)
- Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)
Abstract
The invention discloses a kind of lemon acid albumin, its preparation method and its derived product.The lemon acid albumin of the present invention is that acylation reaction occurs by protein and citric anhydride to be made; it is that generation is substituted by citric anhydride by the hydrogen on the primary amino radical or secondary amino group on protein molecule; there is very strong complexing capacity to metal ion; preparation process uses citric anhydride acylated protein; accessory substance is citric acid; citric acid is human endogenous's property material, nontoxic to human body, there is good intestines and stomach compliance.
Description
Technical field
The invention belongs to biological technical field, more particularly, to a kind of lemon acid albumin, its preparation method and its derivative
Product.
Background technology
Preferable food trace mineral supplement carrier, it is necessary to overcome the gastrointestinal side effect of inorganic salts, there is patient
Compliance, will also can preferably be absorbed by patient, preferably absorbed in duodenum.
Protein can overcome the gastrointestinal side effect of inorganic salts as trace vector, and can make trace element 12
Refer to intestinal absorption.Current existing trace vector is amber acid albumin, EDTA, citric acid, amion acetic acid.For medical mesh
, there is the iron protein succinylate that there is Italfarmaco S.p.A produce of the amber acid albumin for carrier at present.
However, there is following defect in amber acid albumin as trace mineral supplement carrier：First, amber acid albumin is complexed
Complexing amount is relatively low when micro-, and either infant is still grown up to supplement the trace element of suitable dose, it is necessary to once
Property take amber acid albumin complexing micro- medicament dose it is very big, take inconvenience；Second, amber acid albumin is in human body
Intracellular metabolite can also produce substantial amounts of succinic acid, and succinic acid has certain stimulation to eyes, skin, mucous membrane etc.；Third, amber
The side reaction in preparation process of amber acid albumin generates succinic acid, although follow-up have succinic acid to remove technique, technique is cumbersome, and
And still have succinic acid residual.Therefore, it is necessary to a kind of big acylated protein of micro- complexing capacity, the pair in its preparation process
Product and nontoxic to human body non-stimulated in human body metabolism's product, preferably human endogenous's property material.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, the invention provides a kind of lemon acid albumin, its preparation side
Method and its derived product, its object is to by the way that protein and citric anhydride into acylation reaction occur, one kind, which is prepared, to be had
Very strong micro- complexing capacity and accessory substance in preparation process and be human endogenous's property material in human body metabolism's product
Lemon acid albumin, thus solve prior art acylated protein as trace vector complexing capacity is low, in preparation process
Accessory substance and the poisonous technical problem of body metabolism product.
To achieve the above object, according to one aspect of the present invention, there is provided a kind of lemon acid albumin, it is characterised in that
Structural formula with formula (I)：
Wherein, (protein) is protein, and the protein is animal protein, phytoprotein or microprotein
Matter, n is 0 or 1 in formula.
Preferably, the animal protein is the one or more in casein, lactoprotein and/or collagen.
Preferably, the animal protein is casein.
Preferably, the phytoprotein is in soybean protein, germ protein, peanut protein and/or spirulina protein
It is one or more.
Preferably, the phytoprotein is soybean protein isolate.
Preferably, the microprotein is bacterioprotein and/or mycoprotein.
According to another aspect of the present invention, there is provided a kind of preparation method of described lemon acid albumin, the lemon acid egg
It is according to mass ratio 1 in vain by the protein and citric anhydride:0.3~0.6 generation acylation reaction is made.
Preferably, the protein and citric anhydride are according to mass ratio 1:0.4~0.5 reaction is made.
According to another aspect of the present invention, there is provided a kind of derived product of described lemon acid albumin, the derivative
Product is the complex compound of the lemon acid albumin and metal ion.
Preferably, the metal ion includes iron, zinc, strontium, calcium, iodine, selenium, copper, molybdenum, chromium or cobalt.
In general, by the contemplated above technical scheme of the present invention compared with prior art, it can obtain down and show
Beneficial effect：
(1) lemon acid albumin of the invention is that the hydrogen on primary amino radical or secondary amino group on protein molecule is taken by citric anhydride
Generation generation, lemon acid albumin of the invention have very strong complexing capacity to trace element, and corresponding micro- carrying capacity is higher,
The amount of iron load of the lemon acid albumin iron obtained for example with the lemon acid albumin load iron of the present invention is amber acid albumin amount of iron load
1.3~1.5 times；
(2) preparation process of lemon acid albumin of the present invention uses citric anhydride acylated protein, its metabolite
For citric acid, citric acid is human endogenous's property material, nontoxic to human body；
(3) lemon acid albumin produced by the present invention has good intestines and stomach compliance, is carried applied to trace mineral supplement
Can preferably it be absorbed by patient during body；
(4) citric acid protein preparation method of the invention is simple, and protein raw material is easy to get extensively, is applied to micro member
Plain carrier has good market prospects.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of citric acid protein product made from embodiments of the invention 1.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in each embodiment of invention described below
Conflict can is not formed each other to be mutually combined.
The lemon acid albumin of the present invention has formula (I) structure：
Wherein, (protein) is protein, and the protein is animal protein, phytoprotein or microprotein
Matter, n is 0 or 1 in formula.
When the protein is animal protein, it is one kind or more in casein, lactoprotein and/or collagen
Kind, preferably casein；
When the protein is phytoprotein, it is soybean protein, germ protein, peanut protein and/or spirulina
One or more in albumen, preferably soybean protein；
When the protein is microprotein, it is bacterioprotein and/or mycoprotein.
Lemon acid albumin of the present invention is by citric acid by the hydrogen in the primary amine groups or secondary amine on protein molecule
Acid anhydride substitution occurs acylation reaction and generated, and reaction equation is as follows：
In formula, n is 0 or 1.
There are two-COOH by citric anhydride acylation sites in the lemon acid albumin of the present invention, of the invention from structure
Lemon acid albumin has very strong complexing capacity, and the lemon acid albumin of the present invention has both sexes, and its isoelectric point is 4.0~5.5.
The preparation method of lemon acid albumin of the present invention comprises the following steps：
(1) solubilising protein
The protein and water are added in the reactor, is stirred, and pH is adjusted to protein using sodium hydroxide solution
Dissolving is complete, and it is protein clear liquid that separation of solid and liquid, which obtains liquid phase,.
(2) it is acylated
Citric anhydride, wherein protein and citric anhydride are slowly added to by several times in the protein clear liquid obtained to step (1)
Mass ratio be 1:0.3~0.6, preferably 1:0.4~0.5, ensure albumen using sodium hydroxide solution adjustment control pH value of solution
Matter does not separate out, and after citric anhydride adds, continues 0.5~2h of stirring, and hydrochloric acid solution is then slowly added dropwise and controls the pH to be
1.0~5.5, preferable pH scopes are 4.0~5.5；Continue 0.5~2h of stirring, make precipitation complete, separation of solid and liquid, obtain solid phase
For lemon acid protein precipitation.
The mass ratio that wherein acylation reaction occurs for protein and citric anhydride is preferably 1:0.4~0.5, within this range may be used
To obtain the composite result of high acylation degree, low accessory substance.
(3) purify
The lemon acid protein precipitation and water that step (2) obtains are added in the reactor, are stirred, it is molten using sodium hydroxide
Liquid adjusts pH and dissolved completely to lemon acid protein precipitation, and it is citric acid protein solution that separation of solid and liquid, which obtains liquid phase,.While stirring to
It is 1.0~5.5 that hydrochloric acid solution is added in the citric acid protein solution and controls pH value of solution, and preferable pH scopes are 4.0~5.5,
Make precipitation complete, separation of solid and liquid, it is lemon acid albumin crude product to obtain solid phase.Repeat step more than (3) 2 times, obtains lemon acid egg
White wet product.
(4) dry
The lemon acid albumin wet product that step (3) obtains is placed in dry to moisture at 50~60 DEG C of temperature and is less than 5%., obtain
To citric acid protein product.
The derived product of the lemon acid albumin of the present invention, for the lemon acid albumin and the complex compound of metal ion, metal
Ion includes iron, zinc, strontium, calcium, iodine, selenium, copper, molybdenum, chromium or cobalt.
The metal ion of lemon acid albumin produced by the present invention and iron, zinc and calcium is complexed, and utilizes equation below
Calculate the complexing degree of each metal ion species.
Complexing degree=(metal ion total amount-free metal ion amount)/lemon acid albumin addition × 100%
It is embodiment below：
Embodiment 1
Synthesize the raw material needed for 1kg lemon acid albumins：1.0kg caseins, 0.3kg citric anhydrides
Casein：Commercially available, Gansu Hua Ling caseins limited company, lot number HLYX1207061, protein is (with butt
Meter) >=92.0%.
Citric anhydride (reference：The synthesis of the citric anhydrides such as Shi Hao, Li Hanxu, Ding Liming and sign [J] Anhui science and engineering are big
Learn journal (natural science edition), 2006,26 (1), 056-060.)：With agitator, calcium chloride tube, reflux condensing tube
In the four-hole boiling flask of thermometer, a certain amount of anhydrous citric acid, acetic acid and acetic anhydride are added.Controlling reaction temperature 34~40
DEG C, 16~20h of reaction time.After citric acid is completely dissolved, acetic acid is evaporated under reduced pressure out.To remaining solution under conditions of stirring
A certain amount of chloroform is added, white opacity switchs to oily matter, continues stirring and oily matter is converted into white precipitate, take out
Filter cake thing chloroform 2~3 times, product vacuum are dried, and obtain citric anhydride.
1.0kg caseins and 15kg purified waters are added in the reactor, are stirred, 2M NaOH solutions regulation pH to 6.0~
9.0 make dissolving complete.
Citric anhydride 0.3kg is slowly added to by several times, controls pH 6.0~9.0 using 2M sodium hydroxides, citric anhydride addition
After finishing 0.5h, 1M HCl solutions control pH 1.0~4.5 is slowly added dropwise, continues after stirring 0.5h, centrifugation, obtains lemon acid albumin
Precipitation.
Lemon acid protein precipitation and 15kg purified waters are added in the reactor, and 2M sodium hydroxides regulation pH to 6.0~9.0 makes
Dissolving, centrifugation, obtains citric acid protein precipitation solution.Acid solution control pH is added under stirring into citric acid protein precipitation solution
4.0~5.5, make precipitation complete, centrifuge, filtering, obtain lemon acid albumin crude product.Repeat said process 2 times, obtain lemon acid albumin
(wet product).
Lemon acid albumin (wet product) is laid in stainless steel pallet (citric acid protein thickness about 1cm), vacuum is placed in and does
In dry case, control vacuum -0.06MPa~-0.08MPa, 55 DEG C dries 20 hours, obtains lemon acid albumin 1.06kg.Sampling is surveyed
It is 20.5% to obtain lemon acid albumin acylation degree.
The product that embodiment 1 is obtained carries out phenetic analysis using infra-red sepectrometry, obtains infrared spectrum as shown in Figure 1
Figure, as seen from the figure, there is stronger absorption, the absorption for having moderate strength at 3285cm-1, at 2928cm-1 at 1666cm-1
There is the absorption of moderate strength.
Embodiment 2
Synthesize the raw material needed for 1kg lemon acid albumins：1.00kg caseins, 0.45kg citric anhydrides
1.0kg caseins and 10kg purified waters are added in the reactor, are stirred, 2M NaOH solutions regulation pH to 6.0~
9.0 make dissolving complete.
Citric anhydride 0.45kg is slowly added to by several times, controlling pH using 2M sodium hydroxides, citric anhydride adds 6.0~9.0
After adding complete 0.5h, 1M HCl solutions control pH 1.0~4.5 is slowly added dropwise, continues after stirring 0.5h, centrifugation, obtains lemon acid egg
White precipitation.
Lemon acid protein precipitation and 10kg purified waters are added in the reactor, and 2M sodium hydroxides regulation pH to 6.0~9.0 makes
Dissolving, centrifugation, obtains citric acid protein precipitation solution.Acid solution control pH is added under stirring into citric acid protein precipitation solution
4.0~5.5, make precipitation complete, centrifuge, filtering, obtain lemon acid albumin crude product.Repeat said process 2 times, obtain lemon acid albumin
(wet product).
Lemon acid albumin (wet product) is laid in stainless steel pallet (citric acid protein thickness about 1cm), vacuum is placed in and does
In dry case, control vacuum -0.06MPa~-0.08MPa, 55 DEG C dries 20 hours, obtains lemon acid albumin 0.98kg.Sampling is surveyed
Lemon acid albumin acylation degree is 92.8%.
Embodiment 3
Synthesize the raw material needed for 1kg lemon acid albumins：1.00kg caseins, 0.40kg citric anhydrides
1.0kg caseins and 10kg purified waters are added in the reactor, are stirred, 2M NaOH solutions regulation pH to 6.0~
9.0 make dissolving complete.
Citric anhydride 0.40kg is slowly added to by several times, controlling pH using 2M sodium hydroxides, citric anhydride adds 6.0~9.0
After adding complete 0.5h, 1M HCl solutions control pH 1.0~4.5 is slowly added dropwise, continues after stirring 0.5h, centrifugation, obtains lemon acid egg
White precipitation.
Lemon acid protein precipitation and 10kg purified waters are added in the reactor, and 2M sodium hydroxides regulation pH to 6.0~9.0 makes
Dissolving, centrifugation, obtains citric acid protein precipitation solution.Acid solution control pH is added under stirring into citric acid protein precipitation solution
4.0~5.5, make precipitation complete, centrifuge, filtering, obtain lemon acid albumin crude product.Repeat said process 2 times, obtain lemon acid albumin
(wet product).
Lemon acid albumin (wet product) is laid in stainless steel pallet (citric acid protein thickness about 1cm), vacuum is placed in and does
In dry case, control vacuum -0.06MPa~-0.08MPa, 55 DEG C dries 20 hours, obtains lemon acid albumin 0.92kg.Sampling is surveyed
Lemon acid albumin acylation degree is 90.8%.
Embodiment 4
Synthesize the raw material needed for 1kg lemon acid albumins：1.00kg caseins, 0.50kg citric anhydrides
1.0kg caseins and 10kg purified waters are added in the reactor, are stirred, 2M NaOH solutions regulation pH to 6.0~
9.0 make dissolving complete.
Citric anhydride 0.50kg is slowly added to by several times, controlling pH using 2M sodium hydroxides, citric anhydride adds 6.0~9.0
After adding complete 0.5h, 1M HCl solutions control pH 1.0~4.5 is slowly added dropwise, continues after stirring 0.5h, centrifugation, obtains lemon acid egg
White precipitation.
Lemon acid protein precipitation and 10kg purified waters are added in the reactor, and 2M sodium hydroxides regulation pH to 6.0~9.0 makes
Dissolving, centrifugation, obtains citric acid protein precipitation solution.Acid solution control pH is added under stirring into citric acid protein precipitation solution
4.0~5.5, make precipitation complete, centrifuge, filtering, obtain lemon acid albumin crude product.Repeat said process 2 times, obtain lemon acid albumin
(wet product).
Lemon acid albumin (wet product) is laid in stainless steel pallet (citric acid protein thickness about 1cm), vacuum is placed in and does
In dry case, control vacuum -0.06MPa~-0.08MPa, 55 DEG C dries 20 hours, obtains lemon acid albumin 1.06kg.Sampling is surveyed
Lemon acid albumin acylation degree is 96.3%.
Embodiment 5
Synthesize the raw material needed for 1kg lemon acid albumins：1.00kg caseins, 0.60kg citric anhydrides
1.0kg caseins and 10kg purified waters are added in the reactor, are stirred, 2M NaOH solutions regulation pH to 6.0~
9.0 make dissolving complete.
Citric anhydride 0.60kg is slowly added to by several times, controlling pH using 2M sodium hydroxides, citric anhydride adds 6.0~9.0
After adding complete 0.5h, 1M HCl solutions control pH 1.0~4.5 is slowly added dropwise, continues after stirring 0.5h, centrifugation, obtains lemon acid egg
White precipitation.
Lemon acid protein precipitation and 10kg purified waters are added in the reactor, and 2M sodium hydroxides regulation pH to 6.0~9.0 makes
Dissolving, centrifugation, obtains citric acid protein precipitation solution.Acid solution control pH is added under stirring into citric acid protein precipitation solution
4.0~5.5, make precipitation complete, centrifuge, filtering, obtain lemon acid albumin crude product.Repeat said process 2 times, obtain lemon acid albumin
(wet product).
Lemon acid albumin (wet product) is laid in stainless steel pallet (citric acid protein thickness about 1cm), vacuum is placed in and does
In dry case, control vacuum -0.06MPa~-0.08MPa, 55 DEG C dries 20 hours, obtains lemon acid albumin 1.05kg.Sampling is surveyed
Lemon acid albumin acylation degree is 95.5%.
Embodiment 6
Synthesize the raw material needed for 1kg lemon acid albumins：1.0kg soybean protein isolates, 0.30kg citric anhydrides
Add 1.0kg soybean protein isolates and 10kg purified waters, stirring in the reactor, 2M NaOH solutions adjust pH to
6.0~9.0 make dissolving complete.
Citric anhydride 0.30kg is slowly added to by several times, controlling pH using 2M sodium hydroxides, citric anhydride adds 6.0~9.0
After adding complete 0.5h, 1M HCl solutions control pH 1.0~4.5 is slowly added dropwise, continues after stirring 0.5h, centrifugation, obtains lemon acid egg
White precipitation.
Lemon acid protein precipitation and 10kg purified waters are added in the reactor, and 2M sodium hydroxides regulation pH to 6.0~9.0 makes
Dissolving, centrifugation, obtains citric acid protein precipitation solution.Acid solution control pH is added under stirring into citric acid protein precipitation solution
4.0~5.5, make precipitation complete, centrifuge, filtering, obtain lemon acid albumin crude product.Repeat said process 2 times, obtain lemon acid albumin
(wet product).
Lemon acid albumin (wet product) is laid in stainless steel pallet (citric acid protein thickness about 1cm), vacuum is placed in and does
In dry case, control vacuum -0.06MPa~-0.08MPa, 55 DEG C dries 20 hours, obtains lemon acid albumin 1.04kg.Sampling is surveyed
It is 23.8% to obtain lemon acid albumin acylation degree.
Embodiment 7
Synthesize the raw material needed for 1kg lemon acid albumins：1.0kg soybean protein isolates, 0.45kg citric anhydrides
Add 1.0kg soybean protein isolates and 11kg purified waters, stirring in the reactor, 2M NaOH solutions adjust pH to
6.0~9.0 make dissolving complete.
Citric anhydride 0.45kg is slowly added to by several times, controlling pH using 2M sodium hydroxides, citric anhydride adds 6.0~9.0
After adding complete 0.5h, 1M HCl solutions control pH 1.0~4.5 is slowly added dropwise, continues after stirring 0.5h, centrifugation, obtains lemon acid egg
White precipitation.
Lemon acid protein precipitation and 11kg purified waters are added in the reactor, and 2M sodium hydroxides regulation pH to 6.0~9.0 makes
Dissolving, centrifugation, obtains citric acid protein precipitation solution.Acid solution control pH is added under stirring into citric acid protein precipitation solution
4.0~5.5, make precipitation complete, centrifuge, filtering, obtain lemon acid albumin crude product.Repeat said process 2 times, obtain lemon acid albumin
(wet product).
Lemon acid albumin (wet product) is laid in stainless steel pallet (citric acid protein thickness about 1cm), vacuum is placed in and does
In dry case, control vacuum -0.06MPa~-0.08MPa, 55 DEG C dries 20 hours, obtains lemon acid albumin 1.01kg.Sampling is surveyed
It is 90.1% to obtain lemon acid albumin acylation degree.
Embodiment 8
Synthesize the raw material needed for 1kg lemon acid albumins：1.0kg soybean protein isolates, 0.60kg citric anhydrides
Add 1.0kg soybean protein isolates and 15kg purified waters, stirring in the reactor, 2M NaOH solutions adjust pH to
6.0~9.0 make dissolving complete.
Citric anhydride 0.60kg is slowly added to by several times, controlling pH using 2M sodium hydroxides, citric anhydride adds 6.0~9.0
After adding complete 0.5h, 1M HCl solutions control pH 1.0~4.5 is slowly added dropwise, continues after stirring 0.5h, centrifugation, obtains lemon acid egg
White precipitation.
Lemon acid protein precipitation and 15kg purified waters are added in the reactor, and 2M sodium hydroxides regulation pH to 6.0~9.0 makes
Dissolving, centrifugation, obtains citric acid protein precipitation solution.Acid solution control pH is added under stirring into citric acid protein precipitation solution
4.0~5.5, make precipitation complete, centrifuge, filtering, obtain lemon acid albumin crude product.Repeat said process 2 times, obtain lemon acid albumin
(wet product).
Lemon acid albumin (wet product) is laid in stainless steel pallet (citric acid protein thickness about 1cm), vacuum is placed in and does
In dry case, control vacuum -0.06MPa~-0.08MPa, 55 DEG C dries 20 hours, obtains lemon acid albumin 0.99kg.Sampling is surveyed
It is 95.3% to obtain lemon acid albumin acylation degree.
Embodiment 9
1.0kg lemons acid albumin is separately added into the reactor at 3 (to prepare using the methods described of embodiment 2, acylation degree
97%~90%) and 15kg purified waters, stirring, 2M NaOH solutions regulation pH to 6.0~9.0, extremely dissolving completely, obtain citric acid
Protein solution.Citric acid protein solution volume is measured respectively, samples 10ml.
Slowly 4%FeCl is added under stirring into three above reactor respectively3Solution (press by the amount for adding FeCl3 solution
According to lemon acid casein and FeCl3·6H2O weight is than 1:0.34 conversion), 4%ZnCl2Solution (adds ZnCl2The amount of solution is pressed
According to lemon acid casein and ZnCl2Weight is than 1:0.17 conversion), 4%CaCl2Solution (adds CaCl2The amount of solution is according to lemon
Acid casein and CaCl2·6H2O weight is than 1:0.28 conversion), keep pH to add 6.0~9.0 using 2M NaOH solutions
Bi Hou, the volume V of reaction solution in each reactor is determined respectively, take 10ml reaction solutions to determine complexing degree respectively.
1M HCl solutions control pH 1.0~4.5 is added dropwise respectively into each reaction solution, makes precipitation complete, centrifuges, obtain lemon
Acid egg galvanized iron precipitation, citric acid zinc albuminate precipitation, lemon acid albumin calcium precipitate.
Lemon acid albumin iron precipitation, citric acid zinc albuminate are separately added into the reactor in 3 equipped with 15kg purified waters
Precipitation, lemon acid albumin calcium precipitate, stirring, 2M NaOH solutions regulation pH to 6.0~9.0 make dissolving, centrifuge, obtain lemon acid egg
Galvanized iron precipitation solution, citric acid zinc albuminate precipitation solution, lemon acid albumin calcium precipitate solution.Sunk under stirring to lemon acid albumin iron
Added in shallow lake solution, citric acid zinc albuminate precipitation solution, lemon acid albumin calcium precipitate solution 1M HCl solutions control pH 1.0~
4.5, make precipitation complete, centrifuge, filtering, it is thick to obtain lemon acid albumin iron crude product, citric acid zinc albuminate crude product, lemon acid albumin calcium
Product.Repeat said process 2 times.
Lemon acid albumin iron crude product, citric acid zinc albuminate crude product, lemon acid albumin calcium crude product are placed at 50~60 DEG C of temperature
Dry 12~20 hours, obtain lemon acid albumin iron, citric acid zinc albuminate, lemon acid albumin calcium.
Complexing degree assay method：
Extract reaction solution 10ml, add 80ml absolute ethyl alcohols, be sufficiently stirred, centrifuge after take supernatant, with EDTA titration supernatants
Liquid, consumption EDTA titrating solution volumes V2。
Take citric acid protein solution 10ml, add 80ml absolute ethyl alcohols, be sufficiently stirred, centrifuge after take supernatant, use EDTA
Titrate supernatant, consumption EDTA titrating solution volumes V0。
Complexing degree=(metal ion total amount-free metal ion amount)/lemon acid albumin addition × 100%
=M [4%V1*10/V-C(V2-V0)]/1*10/V × 100%
In formula, M be complexation of metal ions molecular weight, g/mol
The 4% metal ion solution concentration to add, mol/l
V1To add the volume of metal ion solution, ml
10 be to determine sampling amount when complexing is spent, ml
C is EDTA titrating solution molar concentrations；mol/l
1 is citric anhydride total amount, kg
V be complex reaction after reaction solution cumulative volume, ml
According to above-mentioned formula, lemon acid albumin iron, citric acid zinc albuminate, lemon acid albumin calcium complexing degree are calculated,
As a result it is as shown in table 1：
The lemon acid albumin iron of table 1, citric acid zinc albuminate, the result of calculation of lemon acid albumin calcium complexing degree
| Title | Lemon acid albumin iron | Citric acid zinc albuminate | Lemon acid albumin calcium |
| Complexing degree g/kg | 56.45 | 61.74 | 66.76 |
Experiment shows：Lemon acid albumin is to Fe3+、Zn2+、Ca2+There is larger complexing degree.
Embodiment 10
Lemon acid albumin is iron standby：
Dissolve lemon acid albumin：1.0kg lemons acid albumin is separately added into the reactor at 4 (using described in embodiment 2
Prepared by method, acylation degree 97%~90%) and 15kg purified waters, stirring, 2M NaOH solutions adjust pH to 6.0~9.0, extremely molten
Solution is complete, obtains citric acid protein solution.
Carry iron：Slowly 4%FeCl is added under stirring in four reactors more than respectively3Solution (adds FeCl3Solution
Amount is according to lemon acid casein and FeCl3·6H2O weight is than 1:0.34 conversion), using 2M NaOH solutions keep pH 6.0~
9.0, add 4%FeCl3Solution total time must not be less than 3h.After addition, pH is adjusted using sodium hydroxide solution, makes pH
Maintain 6~9.4%FeCl3Solution continues 0.5~1h of stirring after being added dropwise, and obtains lemon acid albumin iron crude product solution.
It is refined：3MHCl is added dropwise to above-mentioned citric acid albumen iron crude product solution, regulation pH to 1~4 makes precipitation complete, centrifuged,
Weakly acidic solution washing precipitation.Precipitation is transferred in reactor, adds appropriate 0.01mol/L~1mol/L sodium hydroxide solutions,
After precipitation dissolving completely, 1.5-10.0 μm of filter membrane is crossed, then is made precipitation complete with 3MHCl, regulation pH to 1~4, is centrifuged, washing is heavy
Dried behind shallow lake, produce lemon acid albumin iron.
Lemon acid albumin iron and iron protein succinylate amount of iron load are more as shown in table 2.
The lemon acid albumin iron of table 2 is compared with iron protein succinylate amount of iron load
| Title | Lemon acid albumin iron | Iron protein succinylate |
| Source | It is prepared by the present embodiment | Marketable material medicine |
| Iron-holder | 7.5% | 5.3% |
Experiment shows：Lemon acid albumin iron has higher amount of iron load compared with iron protein succinylate, and lemon acid albumin amount of iron load is
1.4 times of amber acid albumin amount of iron load, thus also complexing power of the provable lemon acid albumin compared with amber acid albumin to ferro element
It is stronger.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, all any modification, equivalent and improvement made within the spirit and principles of the invention etc., all should be included
Within protection scope of the present invention.
Claims (9)
1. a kind of lemon acid albumin as trace vector, it is characterised in that there is the structural formula of formula (I)：
The lemon acid albumin is to be substituted acyl occurs by citric anhydride by the hydrogen in the primary amine groups or secondary amine on protein molecule
Change reaction and generate, the structural formula of the citric anhydride is
Wherein, (protein) is protein, and the protein is animal protein, phytoprotein or microprotein, formula
Middle n is 0 or 1；The animal protein is the one or more in casein, lactoprotein and/or collagen；The citric acid
The acylation degree of albumen is 97%~90%；The lemon acid albumin has both sexes, and its isoelectric point is 4.0~5.5.
2. lemon acid albumin as claimed in claim 1, it is characterised in that the animal protein is casein.
3. lemon acid albumin as claimed in claim 1, it is characterised in that the phytoprotein is soybean protein, peanut egg
One or more in white and/or spirulina protein.
4. lemon acid albumin as claimed in claim 1, it is characterised in that the phytoprotein is soybean protein isolate.
5. lemon acid albumin as claimed in claim 1, it is characterised in that the microprotein is for bacterioprotein and/or very
Mycoprotein.
A kind of 6. preparation method of lemon acid albumin as claimed in any one of claims 1 to 5, wherein, it is characterised in that the lemon
Lemon acid albumin is according to mass ratio 1 by the protein and citric anhydride:0.3~0.6 generation acylation reaction is made.
7. the preparation method of lemon acid albumin as claimed in claim 6, it is characterised in that the protein and citric anhydride are pressed
According to mass ratio 1:0.4~0.5 reaction is made.
8. a kind of derived product of lemon acid albumin as claimed in any one of claims 1 to 5, wherein, it is characterised in that described to spread out
Product is the complex compound of the lemon acid albumin and metal ion.
9. a kind of derived product of lemon acid albumin as claimed in claim 8, it is characterised in that the metal ion includes
Iron, zinc, strontium, calcium, iodine, selenium, copper, molybdenum, chromium or cobalt.
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