CN1211024C - Use of cyclodextrin derivs. in beverage - Google Patents
Use of cyclodextrin derivs. in beverage Download PDFInfo
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- CN1211024C CN1211024C CNB031194427A CN03119442A CN1211024C CN 1211024 C CN1211024 C CN 1211024C CN B031194427 A CNB031194427 A CN B031194427A CN 03119442 A CN03119442 A CN 03119442A CN 1211024 C CN1211024 C CN 1211024C
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Abstract
The present invention relates to an application of a cyclodextrin derivative in the field of a beverage. The cyclodextrin derivative is manual simulation enzyme with glutathione peroxidase activity, the cyclodextrin derivative can effectively remove free radicals in a human body, and the common usage range of the cyclodextrin derivative in the beverage is from 1.0 to 50.0 mg per L. The cyclodextrin derivative which is taken as a functional beverage additive can prevent and treat diseases of cardio-cerebrovascular diseases, liver injury, dermatosis, diabetes, pulmonary infection, rheumatism and rheumatoid, tumour, etc., and the diseases are caused by free radical disturbance. The cyclodextrin derivative can prevent fatigue and delay aging. Because the cyclodextrin derivative has the characteristics of good water solubility, simple preparation process, high yield, high stability and mass production, the cyclodextrin derivative can be added in drinking water, a fruit and vegetable beverage, a milk beverage, a tea beverage, a carbonated beverage, other beverages, etc. Thus, the cyclodextrin derivative which is taken as the functional beverage additive has a wide development prospect.
Description
The present invention relates to field of beverage, particularly, (GPX) the active cyclodextrine derivatives that the present invention relates to have glutathione peroxidase in field of beverage as the application of beverage additive.
Along with the raising of living standards of the people, pursue health, back to nature, advocating natural beverage has become a kind of trend.Therefore, develop natural, nutrition and functionalization beverage additive, become the focus of beverage additive development and consumption.The rise of functional drink and popularization need novel beverage additive product.What functional drink was emphasized is that its composition has the functions such as circadian rhythm, prevent disease and promotion health of abundant adjusting human body.
The microenvironment of simulation zymophore on molecular level, be introduced in the native enzyme the active factor of catalytic reaction, design and composite structure is simple, vigor is stable organic molecule are one of advanced subject in the current natural science field as manual simulation's enzyme.In view of artificial enzyme's molecule may have selectivity identical with native enzyme and catalysis, and itself have advantages such as physico-chemical property is stable, raw material extensively is easy to get, preparation technology is easy, indicating that it has broad application prospects in fields such as chemical industry, zymetology, medicine and pharmacology.For this reason, the U.S. and many European countries all list the manual simulation to enzyme in the development plan of future studies.In recent years, people have set up the imitative enzyme system of many little molecules, as cyclodextrin, crown ether, ring kind, and PAH and porphyrin etc.
Find that after deliberation glutathione peroxidase is an important selenoenzyme in the organism, GPX utilizes glutathione (GSH) catalytic reduction hydroperoxides, thereby has good non-oxidizability.But because this enzyme instability, it is limited to originate, and the molecular weight conference causes shortcomings such as human immunity reaction, has greatly limited the development and application of this enzyme in fields such as medicine, chemical industry, food.We select for use cyclodextrin to simulate GPX, a series of cyclodextrine derivatives that obtained having the GPX activity of success.This compounds has that molecular weight is little, physicochemical property is stable, saturating film good absorbing, have characteristics such as vigor height, good water solubility than other GPX small molecule mimetics, be suitable as beverage additive, its general amount ranges is to contain 1.0～50.0 milligrams in every liter of beverage.
The objective of the invention is to: synthesized a kind of cyclodextrine derivatives of the GPX of having activity, can be used as the functional beverage additive, played preventing fatigue, prevent disease, function in delaying senility.
Therefore, the purpose of this invention is to provide the cyclodextrine derivatives that the present invention relates to and be used for the purposes of beverage as additive;
Another object of the present invention has provided a kind of functional beverage that contains the cyclodextrine derivatives that the present invention relates to.
The general structure of the cyclodextrine derivatives that the present invention relates to is as follows:
Wherein:
Its mother body cyclodextrin structural formula is as follows:
Mother body cyclodextrin can be alpha-cyclodextrin (n=5), beta-schardinger dextrin-(n=6), gamma-cyclodextrin (n=7) in the present invention, and its structure can be used
Or
Represent;
Substituent R
1Can be 2 or 6, substituent R
2Also can be 2 or 6, its condition be R
1Can be on the identical replacement position of the different glucose rings of cyclodextrin, R
2Can be on the identical replacement position of the different glucose rings of cyclodextrin;
R
1Can be-Se ,-Te ,-SeCys ,-TeCys, wherein, Cys represents cysteine, and SeCys represents selenocysteine, and TeCys represents the telluro cysteine;
R
2Can-OH ,-SeO
2H ,-TeO
2H, wherein SeO
2H represents selenous acid, TeO
2H represents tellurous acid.
The structural formula of the preferred cyclodextrine derivatives that the present invention relates to is:
6-SeCD, i.e. 6-selenium bridging cyclodextrin
2-SeCysCD, promptly 2,2 '-N, N '-selenocysteine-selenium bridging cyclodextrin
6-SeCysCD, promptly 6,6 '-N, N '-selenocysteine-selenium bridging cyclodextrin
2-diSeCD, i.e. 2A, 2B-two selenous acid-2A ', 2B '-selenium bridging cyclodextrin
2-diTeCD, i.e. 2A, 2B-two tellurous acid-2A ', 2B '-selenium bridging cyclodextrin
6-diTeCD, i.e. 6A, 6B-two tellurous acid-6A ', 6B '-selenium bridging cyclodextrin
(in the top structural formula, n=5,6,7)
Wherein, CD representative ring dextrin.
The present invention preferably uses the beta-schardinger dextrin-of n=6; More preferably use, for example, 2-Se-β-CD is 2-selenium bridging-beta-schardinger dextrin-, 6-Se-β-CD is 6-selenium bridging-beta-schardinger dextrin-, 2-Te-β-CD is 2-tellurium bridging-beta-schardinger dextrin-, 2-diSe-β-CD is 6A, and 6B-two selenous acid-6A ' 6B ' selenium bridging-beta-schardinger dextrin-, 2-SeCys-β-CD are 2,2 '-N, N '-selenocysteine-selenium bridging-beta-schardinger dextrin-, 6-SeCys-β-CD promptly 6,6 '-N, N '-selenocysteine-selenium bridging-beta-schardinger dextrin-, 2-diTe-β-CD is 6A, 6B-two tellurous acid-6A ', 6B '-tellurium bridging-beta-schardinger dextrin-.
We find that the cyclodextrine derivatives that these that the present invention relates to is had the GPX activity is applied in the beverage, as the functional beverage additive, can play preventing fatigue, prevent disease, function in delaying senility.
Further specify the present invention below by example.It should be understood that example of the present invention is only used for illustrating the present invention, rather than limitation of the present invention, under design prerequisite of the present invention, the present invention is carried out simple modifications and all belong to the scope of protection of present invention.Except as otherwise noted, the percentage among the present invention is percetage by weight.
One. cyclodextrine derivatives prepares example
The compound that the present invention relates to can be by following method preparation.
The preparation method of embodiment 1:NaHSe
With 100mg NaBH
4Be dissolved in the bottle that 5ml water is housed, again the 100mg selenium powder slowly joined NaBH
4Solution in, cover a Jiao Gai who is inserted with syringe needle, can see this moment producing a large amount of gases in the water, and be attended by heat and emit.Because reaction is too violent, so need to carry out in ice bath, with the control reaction speed, its reaction equation is as follows:
Because NaBH
4With H
+Reaction is also with small amount of H
2Se gas produces, and for anti-poisoning, must react in fume hood.After reaction finishes, have in a large number to salt out.NaHSe is oxidation very easily, so should feed N
2Preserve.
Embodiment 2:2-Se-β-CD's (being 2-selenium bridging beta cyclodextrin) is synthetic
Synthetic route is as follows:
(1). 2 sulfonylations of β-CD (product is β-CD-2-position hydroxy benzene sulfonic acid fat, abbreviation 2-OTs-β-CD):
2.0g β-CD is dissolved in 100ml NaOH (0.3mol/L) solution, room temperature drips the acetonitrile solution 5ml of the p-TsCl that contains 2.0g, constantly add 1mol/L NaOH in the dropping process and make pH value of solution＞12.5, dropwised in 3 hours, stirred again 1 hour, add 1mol/L HCl and be neutralized to neutrality, add 100ml methyl alcohol, elimination insoluble matter, pressure reducing and steaming methyl alcohol and most of water are put into 5 ℃ of refrigerator one Zhou Houyou and are salted out to 20ml, filtering the back is that eluant, eluent is through Bio-gel P-2 column chromatography with water, collect first peak, freeze-drying gets product.
(2) .2-OTs-β-CD selenizing:
100mg 2-OTs-β-CD is dissolved in the 5mM phosphate buffer, logical high purity nitrogen deoxidation, add 100 μ l 1MNaHSe, 60 ℃ were reacted 36 hours, and made reaction system fully be exposed to oxidation in the air then, the centrifugal selenium that removes, supernatant is through Bio-gel P-2 post (5.0 * 50cm) separation and purification, 254nm ultraviolet monitoring collection first peak, freeze-drying, it is inferior to give a baby a bath on the third day after its birth with acetone, and vacuum drying gets pale yellow powder title compound 2-Se-β-CD.
Embodiment 3:6-Se-β-2D (being 6-selenium bridging beta cyclodextrin) synthetic method
Synthetic route is as follows:
(1) (6-OTs-β's-CD) is synthetic for .6-tolysulfonyl-beta-schardinger dextrin-
β-CD recrystallization back was in 120 ℃ of vacuum drying one day, and pyridine refluxed 17 hours with KOH, used the BaO drying more whole night, the time spent air-distillation.P-TsCl 3.6g is dissolved in pyridine 10mL, slowly the pyridine solution of p-TsCl is added drop-wise to 27g in the pyridine solution of β-CD under condition of ice bath, and 160mL dropwised the back room temperature reaction 24 hours.Reaction finishes and uses acetone precipitation, by filter, and pressed powder water recrystallization.Soak with ether at last, product is a palm fibre white.
(2) .6-OTs-β-CD selenizing and separation and purification
100mg 6-OTs-β-CD is dissolved in 1mL 50mM PBS and the 1mL DMF mixed solution, logical high purity nitrogen deoxidation, add 100 μ L 1M NaHSe, 60 ℃ were reacted 36 hours, and made reaction system fully be exposed to oxidation in the air then, the centrifugal selenium that removes, supernatant is through Biogel P-2 column separating purification, and the 254nm ultraviolet monitoring is collected first peak, freeze-drying, with acetone give a baby a bath on the third day after its birth time pale yellow powder.The P-2 post separates and three absworption peaks occur, and first peak is selenium bridging β-CD absworption peak (being the target product peak), and second peak is single selenium hydrogenated beta-CD, and the 3rd peak is unreacted 6-OTs-β-CD and small molecular weight impurity peak.
Embodiment 4:2-Te-β-CD (being 2-tellurium bridging beta cyclodextrin) and 6-Te-β-CD (being 6-tellurium bridging beta cyclodextrin) synthetic method
(1) (6-OTs-β-CD) synthetic sees embodiment 3 to .6-position-tolysulfonyl-beta-schardinger dextrin-
(2) (2-OTs-β-CD) synthetic sees embodiment 2 to .2-position-tolysulfonyl-beta-schardinger dextrin-
(3). the preparation of sodium hydrogen telluride (NaTeH)
With 3.5g tellurium powder and 2g NaBH
4Join in the 70mL absolute ethyl alcohol, have gas to produce, and be attended by heat and emit.Logical nitrogen number minute makes system keep anaerobic.Little fire added hot reflux about 1 hour, tellurium powder and NaBH
4All dissolvings, solution is aubergine.Be cooled to room temperature, add 4.5mL anaerobic glacial acetic acid, be heated to boiling.Have black precipitate to produce, solution is water white transparency.After the cooling, solution can use.
(4) synthetic (the 6-Te-β-CD) of .6-position-tellurium bridging β-CD
100mg 6-OTs-β-CD is dissolved in the mixed solution of 0.5mL 50mM PBS (pH 7) and 0.5mL DMF, logical high purity nitrogen deoxygenation 25 minutes, add the above-mentioned NaHTe solution of 2mL, 60 ℃ of reactions are after 36 hours, make reaction system fully be exposed to oxidation in the air, have black precipitate to produce, solution is yellow.Centrifugal 10 minutes of 6000rpm, (Φ 5 * A50cm) column separating purifications are done wash-out night with deionized water to yellow solution through Sephadex G-25, the 254nm ultraviolet monitoring, collect first peak solution, it is inferior to give a baby a bath on the third day after its birth with acetone after the freeze-drying, gets the buff powder target compound after the drying.
(5) synthetic (the 2-Te-β-CD) of .2-position-tellurium bridging β-CD
100mg 2-OTs-β-CD is dissolved in 1mL 50mM PBS (pH7) solution, and logical high purity nitrogen deoxidation 25 minutes adds the above-mentioned NaHTe solution of 2mL, and 60 ℃ were reacted 36 hours.Make reaction system fully be exposed to oxidation in the air then, have black precipitate to produce, solution is yellow.Centrifugal 10 minutes of 6000rpm, (Φ 5 * A50cm) column separating purifications are made eluent with deionized water to yellow solution through Sephadex G-25, the 254nm ultraviolet monitoring, collect first peak solution, it is inferior to give a baby a bath on the third day after its birth with acetone after the freeze-drying, gets the buff powder target compound after the drying.
Embodiment 5:2-SeCys-β-CD (promptly 2,2 '-N, N '-selenocysteine-selenium bridging-beta-schardinger dextrin-) synthetic method
(1). and 2 sulfonylations of β-CD (product is β-CD-2-position hydroxy benzene sulfonic acid fat, abbreviation 2-OTs-β-CD)
2.0g β-CD is dissolved in 100ml NaOH (0.3mol/L) solution, room temperature drips the acetonitrile solution 5ml that contains 2.0g p-TsCl, constantly add 1mol/L NaOH in the dropping process and make pH value of solution＞12.5,3h dropwises and stirs 1h again, add 1mol/L HCl and be neutralized to neutrality, add 100ml methyl alcohol, the elimination insoluble matter, pressure reducing and steaming methyl alcohol and most of water are to 20ml, put into 5 ℃ of refrigerator one Zhou Houyou and salt out, filter the back and be eluant, eluent, collect first peak through Bio-gel P-2 column chromatography with water, freeze-drying gets product.
(2) (2-I-β's-CD) is synthetic for .2-iodo-beta-schardinger dextrin-
DMF is with phosphorus pentoxide dry a couple of days, time spent decompression distillation.2-OTs-β-CD 8.5g is dissolved in DMF (50mL), adds KI (6.8g) then, feeds N in the reactant liquor
2To get rid of O
2Under air-proof condition, in 80-90 ℃ of vigorous stirring reaction 8 hours.Reaction finishes and adds chloroform precipitation iodo β-CD, and suction filtration with the dissolving of solid water, adds the tetrachloro-ethylene postprecipitation, collects solid.
(3) .2,2 '-N, synthetic (the 2-SeCys-β-CD) of N '-selenocysteine-selenium bridging-beta-schardinger dextrin-
SeCyss (selenocystine) 14mg is dissolved in 6mL water, adds 17mg Na then
2CO
3, again this solution is added to the DMF solution 510mg of 2-I-β-CD, in 65 ℃ of reactions 20 hours under oxygen free condition.Reactant is handled: oxidation in air, centrifugal, supernatant through Sephadex G-25 (Φ 5 * A50cm) column chromatographies are collected first peak, freeze-drying, freeze-dried powder is faint yellow target compound.
Embodiment 6:2-diTe-β-CD (being 6A, 6B-two tellurous acid-6A ', 6B '-tellurium bridging beta cyclodextrin) synthetic method
(1) .6A, (be 6A, 6B-Capped-β's-CD) is synthetic for 6B-cap company-β-CD
β-CD 7.0g is dissolved in the 50mL pyridine.1, the pyridine solution 1.28g of benzene sulfonyl chloride between 3-slowly is added drop-wise under room temperature in the solution of β-CD, and room temperature reaction is 20 hours under the vigorous stirring.Reaction finishes, and decompression distillation is soaked whole night with acetone, and suction filtration is dry under vacuum.Crude product 8g joins 50mL H
2O-ethanol (3: 2) filters insoluble matter, under agitation dropwise drips 700mL CH
3CN-H
2O (6: 1) filters white precipitate, the filtrate decompression distillation.End-product is dissolved in the ethanol water of 60mL 20%, adds 50mL DEAE-52, and stirring at room 0.5 hour is filtered, and the filtrate decompression distillation obtains white brown product.
(2). synthetic 6A, 6B-two tellurous acid-6A ', 6B '-tellurium bridging-beta-schardinger dextrin-(6-diTe-β-CD)
6A, 6B-Capped-β-CD (100mg) is dissolved in the phosphate buffer of the 50mM pH7.0 of 1mL, adds 1mLDMF and urgees molten.The logical nitrogen of reaction mixture 20 minutes is airtight to get rid of oxygen.Add 100 μ LNaHTe solution with syringe then, under nitrogen protection, in 60 ℃ of reactions 36 hours.Oxidation in air, centrifugal, supernatant has three peaks to occur through Sephadex G-25 post purifying, collects first peak, freeze-drying, freeze-dried powder is faint yellow target compound.
Embodiment 7:6-SeCys-β-CD (6,6 '-N, N '-selenocysteine-selenium bridging-beta-schardinger dextrin-) synthetic method
(1) (6-OTs-β's-CD) is synthetic for .6-tolysulfonyl-beta-schardinger dextrin-
β-CD recrystallization back was in 120 ℃ of vacuum drying one day.Pyridine refluxed 17 hours with KOH, used the BaO drying more whole night, the time spent air-distillation.P-TsCl 3.6g is dissolved in pyridine 10mL, slowly the pyridine solution of p-TsCl is added drop-wise to 27g in the pyridine solution of β-CD under condition of ice bath, and 160mL dropwised the back room temperature reaction 24 hours.Reaction finishes and uses acetone precipitation, suction filtration, pressed powder water recrystallization.Soak with ether at last, product is a palm fibre white.
(2) (6-I-β's-CD) is synthetic for .6-iodo-beta-schardinger dextrin-
DMF is with phosphorus pentoxide dry a couple of days, time spent decompression distillation.6-OTs-β-CD 8.5g is dissolved in DMF (50mL), adds KI (6.8g) then, feeds N in the reactant liquor
2To get rid of O
2Under air-proof condition, in 80-90 ℃ of vigorous stirring reaction 4 hours.Reaction finishes and adds chloroform precipitation iodo β-CD, and suction filtration with the dissolving of solid water, adds the tetrachloro-ethylene postprecipitation, collects solid.
(3) .6,6 '-N, synthetic (the 6-SeCys-β-CD) of N '-selenocysteine-selenium bridging-beta-schardinger dextrin-
(10mg 0.03mmol) is dissolved in 4mL water to SeCyss, adds 13mg (0.12mmol) Na then
2CO
3, again this solution is added to 6-I-β-CD DMF solution (400mg, 32mmol), in 65 ℃ under oxygen free condition the reaction 20 hours.Reactant is handled: oxidation in air, centrifugal, supernatant through Sephadex G-25 (Φ 5 * A50cm) column chromatographies are collected first and are fallen, freeze-drying, freeze-dried powder is faint yellow target compound.
Embodiment 8:2-diSe-β-CD (6A, 6B-two selenous acid-6A ', 6B '-selenium bridging beta cyclodextrin) synthetic method
(1). synthetic 6A, 6B-two selenous acid-6A ', 6B '-selenium bridging-beta-schardinger dextrin-(6-diSe-β-CD)
6A, 6B-Capped-β-CD (100mg) is dissolved in the phosphate buffer of the 50mM pH7.0 of 1mL, adds 1mL DMF and urgees molten.The logical nitrogen of reaction mixture 20 minutes is airtight to get rid of oxygen.Add 100 μ L NaHSe solution with syringe then, under nitrogen protection, in 60 ℃ of reactions 36 hours.Oxidation in air, centrifugal, supernatant has three peaks to occur through SephadexG-25 post purifying, collects first peak, freeze-drying, freeze-dried powder is faint yellow target compound.
Two. following is that example explanation cyclodextrine derivatives is applied to the preparation process in the beverage with drinking water, beverage made of fruits or vegetables and tea beverage respectively
1. the preparation of drinking water (preparation technology's flow chart is seen accompanying drawing 1)
Technology point:
(1) away from the underground water source of 500 meters deep-wells of employing of city, industrial and mining area.
(2) ten thousand/micron counter-infiltration: thoroughly removed harmful substance in the water: chloroform, heavy metal ion, bacterium, fluorescent thing, radiation material etc.
Add cyclodextrine derivatives after the counter-infiltration of (3) ten thousand/micron.
2. beverage made of fruits or vegetables preparation
2.1 the preparation of fruit drink (preparation technology's flow chart is seen accompanying drawing 2)
Technology point
(1) choosing fruit: raw material really answers seven to medium well, does not have and rots, goes bad and the worm-eaten phenomenon.
(2) cleaning and sterilizing: will carry out disinfection in 0.5 hour with the liquor potassic permanganate immersion again after raw material is really cleaned.
(3) weighing for the first time: title be fruit flesh weight, as the benchmark of allotment.
(4) making beating: add partial supplementary material before the making beating.
(5) squeeze the juice: squeeze the juice and homogenizing process all adopts colloid mill, therefore will note the adjustment in its gap.
(6) homogeneous: adopt colloid mill.
(7) weighing for the second time: title be the weight of fruit juice.
(8) allotment: add remainder auxiliary material (adding cyclodextrine derivatives this moment).
(9) pre-sterilizing: measure the pH value of juice before the pre-sterilizing with accurate pH test paper, the pre-sterilizing operation has the purpose of the degassing.
(10) determining of technological parameter: adopt experiment of single factor and multifactor orthogonal experiment method to draw.
2.2 the preparation of juice beverage
1) preparation of vegetable juice (preparation technology's flow chart is seen accompanying drawing 3)
2) preparation of vegetable juice series beverage product (preparation technology's flow chart is seen accompanying drawing 4)
Technology point
(1) select vegetables: the raw material vegetables answer seven to medium well, do not have to rot, go bad and the worm-eaten phenomenon.
(2) cleaning heat boils: the raw material vegetables want hot water to boil to carry out disinfection after cleaning.
(3) fragmentation: vegetables are broken as far as possible.
(4) squeeze the juice: the process of squeezing the juice all adopts colloid mill.
(5) before sterilization, add cyclodextrine derivatives.
2.3 the preparation of tea beverage (preparation technology's flow chart is seen accompanying drawing 5)
The production technology of modern tea beverage has two main points: hot canning and cold clarification.
Three. with 2-Se-β-CD is that the bright cyclodextrine derivatives of illustration is used for beverage and prevents fatigue, function in delaying senility
1. experimental technique
MTT (methyl tetrazolium blue) method is measured cell survival rate cell in human body metabolism and is always being upgraded, and the length of cell survival time has reflected the degree of human senility.It is the bluish violet crystal that succinate dehydrogenase in the living cells (SDH) can reduce MTT, and this material is at OD
490Characteristic absorption peak is arranged.Have only the SDH in the living cells that vigor is just arranged.
The every hole of culture plate adds the 40 μ l MTT reactant liquors (PBS2ml that adds 10mmol/L pH7.4 among the MTT 10mg, molten back 0.22 μ m membrane filtration) 37 ℃ of insulations are 4 hours, in 1500rpm centrifugal 10 minutes again, abandon supernatant, add methyl-sulfoxide (DMSO) 600 μ l, vibrate and survey OD after 10 minutes
490
2. result
Concentration OD
490
0.0μM 0.541±0.092
4.0μM
* 2.570±0.765
20.0μM
* 3.468±0.366
100μM
** 4.239±0.831
*P＜0.05，
**P＜0.01 n＝6
3. conclusion: pair cell has significant protective effect after adding 2-Se-β-CD as can be seen by above data, can prevent fatigue, delay senility.
Four. cyclodextrine derivatives is used for the prophylactic effect of beverage:
GPX has good non-oxidizability, is distributed in the cytosol of cell and the mitochondria and eliminates H
2O
2And hydroperoxides, alleviate and stop lipid peroxidation.Therefore the dextrin derivative that has the GPX vigor can be used for the treatment of the disease that cardiovascular and cerebrovascular disease, hepar damnification, diabetes, pulmonary infection, rheumatism and rheumatoid disease, skin disease, tumour etc. are caused by free radical.
In sum, cyclodextrine derivatives preparation technology of the present invention is simple, and the productive rate height can be produced in a large number, and the immunogenicity that have higher GPX activity, good stability, can overcome native enzyme is big, crosses the film difficulty, shortcomings such as instability.The disease that cardiovascular and cerebrovascular disease, hepar damnification, skin disease, diabetes, pulmonary infection, rheumatism and rheumatoid disease, tumour etc. are caused by the free radical disorder can be prevented and treat to long-term drinking.And the effect that the fatigue of preventing is arranged, delay senility.Aspect the functional beverage additive, vast potential for future development is being arranged.
Claims (11)
1. as the application of beverage additive, the structure of described cyclodextrine derivatives is in beverage for a cyclodextrine derivatives:
Wherein:
The mother body cyclodextrin structural formula is as follows:
Mother body cyclodextrin can be alpha-cyclodextrin (n=5), beta-schardinger dextrin-(n=6), gamma-cyclodextrin (n=7), and its structure is used
Or
Represent;
Substituent R
1Can be at 2 or 6, substituent R
2Also can be that its condition is R at 2 or 6
1Be on the identical replacement position of the different glucose rings of cyclodextrin, R
2Be on the identical replacement position of the different glucose rings of cyclodextrin;
R
1Can be-Se ,-Te ,-SeCys ,-TeCys, wherein, Cys represents cysteine, and SeCys represents selenocysteine, and TeCys represents the telluro cysteine.
R
2Can-OH ,-SeO
2H ,-TeO
2H, wherein SeO
2H represents selenous acid, TeO
2H represents tellurous acid.
2. according to the application of claim 1, wherein cyclodextrine derivatives is selected from:
2,2 '-N, N '-selenocysteine-selenium bridging cyclodextrin
Smart
6A, 6B-two selenous acid-6A ', 6B '-selenium bridging ring
Dextrin
2,2 '-N, N '-telluro cysteine-tellurium bridging cyclodextrin
Dextrin
Dextrin
Wherein: n=5,6,7.
3. according to the application of claim 2, wherein select the cyclodextrine derivatives of n=6 for use.
4. according to the application of claim 3, wherein cyclodextrine derivatives is selected from 2-selenium bridging-beta-schardinger dextrin-, 6-selenium bridging-beta-schardinger dextrin-, 2-tellurium bridging-beta-schardinger dextrin-, 6A, 6B-two selenous acid-6A ', 6B '-selenium bridging-beta-schardinger dextrin-, 2,2 '-N, N '-selenocysteine-selenium bridging-beta-schardinger dextrin-, 6,6 '-N, N '-selenocysteine-selenium bridging-beta-schardinger dextrin-, or 6A, 6B-two tellurous acid-6A ', 6B '-tellurium bridging-beta-schardinger dextrin-.
5. beverage composition for treating dental erosion, it contains conventional carrier or the auxiliary material that uses in following cyclodextrine derivatives and the beverage, and the structure of this cyclodextrine derivatives is
Wherein:
The mother body cyclodextrin structural formula is as follows:
Mother body cyclodextrin can be alpha-cyclodextrin (n=5), beta-schardinger dextrin-(n=6), gamma-cyclodextrin (n=7), and its structure is used
Or
Represent;
Substituent R
1Can be at 2 or 6, substituent R
2Also can be that its condition is R at 2 or 6
1Be on the identical replacement position of the different glucose rings of cyclodextrin, R
2Be on the identical replacement position of the different glucose rings of cyclodextrin;
R
1Can be-Se ,-Te ,-SeCys ,-TeCys, wherein, Cys represents cysteine, and SeCys represents selenocysteine, and TeCys represents the telluro cysteine;
R
2Can-OH ,-SeO
2H ,-TeO
2H, wherein SeO
2H represents selenous acid, TeO
2H represents tellurous acid.
6. according to the composition of claim 5, wherein cyclodextrine derivatives is selected from:
2A, 2B-two selenous acid-2A ', 2B '-selenium bridging
Cyclodextrin
Cyclodextrin
2-tellurium bridging cyclodextrin
2A, 2B-two tellurous acid-2A ', 2B '-tellurium bridging
Cyclodextrin, perhaps
Cyclodextrin,
Wherein: n=5,6,7.
7. according to the composition of claim 6, wherein select the cyclodextrine derivatives of n=6 for use.
8. according to the composition of claim 7, wherein cyclodextrine derivatives is selected from 2-selenium bridging-beta-schardinger dextrin-, 6-selenium bridging-beta-schardinger dextrin-, 2-tellurium bridging-beta-schardinger dextrin-, 6A, 6B-selenous acid-6A ', 6B '-selenium bridging-beta-schardinger dextrin-, 2,2 '-N, N '-telluro cysteine-tellurium bridging cyclodextrin-beta-schardinger dextrin-, 6,6 '-N, N '-telluro cysteine-tellurium bridging cyclodextrin-beta-schardinger dextrin-, or 6A, 6B-two tellurous acid-6A ', 6B '-tellurium bridging-beta-schardinger dextrin-.
9. according to the beverage composition for treating dental erosion of one of claim 5-8, the weight content scope of wherein said cyclodextrine derivatives in beverage is to contain 1.0～50.0 milligrams in every liter of beverage.
10. according to the beverage composition for treating dental erosion of one of claim 5-8, it can be drinking water, beverage made of fruits or vegetables, milk beverage, tea beverage, soda or other drink form.
11. beverage composition for treating dental erosion according to claim 9, it can be drinking water, beverage made of fruits or vegetables, milk beverage, tea beverage, soda or other drink form.
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| CNB031194427A CN1211024C (en) | 2003-03-13 | 2003-03-13 | Use of cyclodextrin derivs. in beverage |
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| CNB031194427A CN1211024C (en) | 2003-03-13 | 2003-03-13 | Use of cyclodextrin derivs. in beverage |
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| CN1211024C true CN1211024C (en) | 2005-07-20 |
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| CN102675486A (en) * | 2011-03-15 | 2012-09-19 | 吉林大学 | Method for producing selenylation cyclodextrin on large scale |
| CN105878274A (en) * | 2016-04-08 | 2016-08-24 | 吉林大学 | Breast cancer radiotherapy sensitization medicine and preparation method thereof |
| CN115677548B (en) * | 2022-11-16 | 2024-04-09 | 湖南农业大学 | Efficient synthesis method of selenomethionine |
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