CN103880724A - Ethoxybenzaldehyde L-cysteine schiff base as well as preparation method and application thereof - Google Patents
Ethoxybenzaldehyde L-cysteine schiff base as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN103880724A CN103880724A CN201410148587.0A CN201410148587A CN103880724A CN 103880724 A CN103880724 A CN 103880724A CN 201410148587 A CN201410148587 A CN 201410148587A CN 103880724 A CN103880724 A CN 103880724A
- Authority
- CN
- China
- Prior art keywords
- cys
- ethoxybenzaldehyde
- schiff
- base
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- -1 Ethoxybenzaldehyde L-cysteine schiff base Chemical class 0.000 title abstract description 11
- 239000002262 Schiff base Substances 0.000 title abstract description 7
- JRHHJNMASOIRDS-UHFFFAOYSA-N 4-ethoxybenzaldehyde Chemical compound CCOC1=CC=C(C=O)C=C1 JRHHJNMASOIRDS-UHFFFAOYSA-N 0.000 claims abstract description 71
- 240000007817 Olea europaea Species 0.000 claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 239000012265 solid product Substances 0.000 claims abstract description 4
- 239000002244 precipitate Substances 0.000 claims abstract description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 14
- 238000004321 preservation Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000002242 deionisation method Methods 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 2
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 abstract description 75
- 239000000243 solution Substances 0.000 abstract description 9
- 230000003287 optical effect Effects 0.000 abstract description 3
- 235000013878 L-cysteine Nutrition 0.000 abstract 4
- 239000004201 L-cysteine Substances 0.000 abstract 4
- JYEJPUBLULIIQN-DKWTVANSSA-N (2r)-2-amino-3-sulfanylpropanoic acid;ethanol Chemical compound CCO.SC[C@H](N)C(O)=O JYEJPUBLULIIQN-DKWTVANSSA-N 0.000 abstract 1
- 239000003755 preservative agent Substances 0.000 abstract 1
- 239000002585 base Substances 0.000 description 45
- 230000000694 effects Effects 0.000 description 24
- 235000013399 edible fruits Nutrition 0.000 description 23
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- 238000011160 research Methods 0.000 description 12
- 102000004190 Enzymes Human genes 0.000 description 9
- 108090000790 Enzymes Proteins 0.000 description 9
- 210000005229 liver cell Anatomy 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 102000003425 Tyrosinase Human genes 0.000 description 7
- 108060008724 Tyrosinase Proteins 0.000 description 7
- 230000005764 inhibitory process Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 6
- 235000011187 glycerol Nutrition 0.000 description 6
- 239000012636 effector Substances 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 231100000419 toxicity Toxicity 0.000 description 5
- 230000001988 toxicity Effects 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 235000021022 fresh fruits Nutrition 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 230000000452 restraining effect Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 239000006144 Dulbecco’s modified Eagle's medium Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000845 anti-microbial effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 231100000135 cytotoxicity Toxicity 0.000 description 3
- 230000003013 cytotoxicity Effects 0.000 description 3
- 239000000796 flavoring agent Substances 0.000 description 3
- 235000019634 flavors Nutrition 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 230000012010 growth Effects 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 230000000050 nutritive effect Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- BINPUCCYCNPQRZ-UHFFFAOYSA-N 4-(furan-2-carbonyl)pyrazol-3-one Chemical compound O1C(=CC=C1)C(=O)C1=CN=NC1=O BINPUCCYCNPQRZ-UHFFFAOYSA-N 0.000 description 2
- 244000012254 Canarium album Species 0.000 description 2
- 235000009103 Canarium album Nutrition 0.000 description 2
- 102000004316 Oxidoreductases Human genes 0.000 description 2
- 108090000854 Oxidoreductases Proteins 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009395 breeding Methods 0.000 description 2
- 230000001488 breeding effect Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000010261 cell growth Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000012258 culturing Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000000119 electrospray ionisation mass spectrum Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000000968 intestinal effect Effects 0.000 description 2
- 229940040145 liniment Drugs 0.000 description 2
- 239000000865 liniment Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 235000019633 pungent taste Nutrition 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- QTENRWWVYAAPBI-YCRXJPFRSA-N streptomycin sulfate Chemical compound OS(O)(=O)=O.OS(O)(=O)=O.OS(O)(=O)=O.CN[C@H]1[C@H](O)[C@@H](O)[C@H](CO)O[C@H]1O[C@@H]1[C@](C=O)(O)[C@H](C)O[C@H]1O[C@@H]1[C@@H](N=C(N)N)[C@H](O)[C@@H](N=C(N)N)[C@H](O)[C@H]1O.CN[C@H]1[C@H](O)[C@@H](O)[C@H](CO)O[C@H]1O[C@@H]1[C@](C=O)(O)[C@H](C)O[C@H]1O[C@@H]1[C@@H](N=C(N)N)[C@H](O)[C@@H](N=C(N)N)[C@H](O)[C@H]1O QTENRWWVYAAPBI-YCRXJPFRSA-N 0.000 description 2
- 231100000041 toxicology testing Toxicity 0.000 description 2
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 2
- KKEUGGZODLCCTR-UHFFFAOYSA-N 3-methyl-5-(trifluoromethyl)-4h-1,2-oxazol-5-ol Chemical compound CC1=NOC(O)(C(F)(F)F)C1 KKEUGGZODLCCTR-UHFFFAOYSA-N 0.000 description 1
- DZLOUWYGNATKKZ-UHFFFAOYSA-N 4-ethoxycinnamic acid Natural products CCOC1=CC=C(C=CC(O)=O)C=C1 DZLOUWYGNATKKZ-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 244000063299 Bacillus subtilis Species 0.000 description 1
- 241001436672 Bhatia Species 0.000 description 1
- 240000007124 Brassica oleracea Species 0.000 description 1
- 235000003899 Brassica oleracea var acephala Nutrition 0.000 description 1
- 235000011301 Brassica oleracea var capitata Nutrition 0.000 description 1
- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 description 1
- 241000208231 Bursera Species 0.000 description 1
- 241000644798 Canarium <sea snail> Species 0.000 description 1
- 102000030523 Catechol oxidase Human genes 0.000 description 1
- 108010031396 Catechol oxidase Proteins 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 238000004252 FT/ICR mass spectrometry Methods 0.000 description 1
- 241000366676 Justicia pectoralis Species 0.000 description 1
- WTDRDQBEARUVNC-LURJTMIESA-N L-DOPA Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-LURJTMIESA-N 0.000 description 1
- WTDRDQBEARUVNC-UHFFFAOYSA-N L-Dopa Natural products OC(=O)C(N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-UHFFFAOYSA-N 0.000 description 1
- 206010027336 Menstruation delayed Diseases 0.000 description 1
- 229930182555 Penicillin Natural products 0.000 description 1
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 230000001708 anti-dyslipidemic effect Effects 0.000 description 1
- 230000003260 anti-sepsis Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 235000021167 banquet Nutrition 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 235000002333 black apple Nutrition 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 244000309466 calf Species 0.000 description 1
- TWFZGCMQGLPBSX-UHFFFAOYSA-N carbendazim Chemical compound C1=CC=C2NC(NC(=O)OC)=NC2=C1 TWFZGCMQGLPBSX-UHFFFAOYSA-N 0.000 description 1
- 239000006285 cell suspension Substances 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229940042396 direct acting antivirals thiosemicarbazones Drugs 0.000 description 1
- 231100000673 dose–response relationship Toxicity 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 235000021038 drupes Nutrition 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 239000002532 enzyme inhibitor Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 235000012055 fruits and vegetables Nutrition 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000304 hepatotoxicity Toxicity 0.000 description 1
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007056 liver toxicity Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- VMGAPWLDMVPYIA-HIDZBRGKSA-N n'-amino-n-iminomethanimidamide Chemical compound N\N=C\N=N VMGAPWLDMVPYIA-HIDZBRGKSA-N 0.000 description 1
- 231100001083 no cytotoxicity Toxicity 0.000 description 1
- 231100000957 no side effect Toxicity 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 235000008935 nutritious Nutrition 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 229940049954 penicillin Drugs 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000013641 positive control Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- BOLDJAUMGUJJKM-LSDHHAIUSA-N renifolin D Natural products CC(=C)[C@@H]1Cc2c(O)c(O)ccc2[C@H]1CC(=O)c3ccc(O)cc3O BOLDJAUMGUJJKM-LSDHHAIUSA-N 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000012747 synergistic agent Substances 0.000 description 1
- SRVJKTDHMYAMHA-WUXMJOGZSA-N thioacetazone Chemical compound CC(=O)NC1=CC=C(\C=N\NC(N)=S)C=C1 SRVJKTDHMYAMHA-WUXMJOGZSA-N 0.000 description 1
- 150000003584 thiosemicarbazones Chemical class 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 229960005486 vaccine Drugs 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Images
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
对乙氧基苯甲醛L-半胱氨酸席夫碱及其制备方法与应用，涉及对乙氧基苯甲醛L-半胱氨酸席夫碱。所述对乙氧基苯甲醛L-半胱氨酸席夫碱的相对分子量为253.3174，其旋光性为左旋，用“L”表示。制备方法：将L-半胱氨酸加入水中溶解，制成L-半胱氨酸水溶液；在L-半胱氨酸水溶液中加入无水乙醇，得到L-半胱氨酸的乙醇溶液；在L-半胱氨酸乙醇溶液中加入对乙氧基苯甲醛和无水乙醇后油浴加热，再直接抽滤后，用无水乙醇冲洗沉淀，然后用乙酸乙酯和水重结晶纯化，即得白色固体产物对乙氧基苯甲醛L-半胱氨酸席夫碱，产率75.6%～78.3%。所述对乙氧基苯甲醛L-半胱氨酸席夫碱可在制备橄榄保鲜剂中应用。The p-ethoxybenzaldehyde L-cysteine Schiff base and its preparation method and application relate to the p-ethoxybenzaldehyde L-cysteine Schiff base. The relative molecular weight of the p-ethoxybenzaldehyde L-cysteine Schiff base is 253.3174, and its optical rotation is left-handed, represented by "L". Preparation method: Dissolve L-cysteine in water to make an aqueous solution of L-cysteine; add absolute ethanol to the aqueous solution of L-cysteine to obtain an ethanol solution of L-cysteine; Add p-ethoxybenzaldehyde and absolute ethanol to the L-cysteine ethanol solution, heat in an oil bath, and then directly suction filter, wash the precipitate with absolute ethanol, and then recrystallize and purify with ethyl acetate and water, that is The white solid product p-ethoxybenzaldehyde L-cysteine Schiff base was obtained, and the yield was 75.6%-78.3%. The p-ethoxybenzaldehyde L-cysteine Schiff base can be used in the preparation of olive preservatives.
Description
Technical field
The present invention relates to p-ethoxybenzaldehyde Cys Schiff's base, especially relate to p-ethoxybenzaldehyde Cys Schiff's base and preparation method thereof and application.
Background technology
Olive (Canarium album) is is the perennial evergreen shrub of Bursera family Canarium
[1]olive is dark green drupe, be commonly called as Chinese olive, Bai Lan, Huang Lan, black apple, for the peculiar fruit of south China, its fruits nutrition is abundant, sweet-puckery flavor and with fragrance, have Appetizing spleen-tonifying, fat-reducing slimming, wet one's whistle, promote the production of body fluid, pharmaceutical use and the health care function such as removing toxic substances, be on New Year's Day or other festivals with the standing good fruit of banquet.Olive fruits unique flavor, fresh fruit is chewed carefully, and has the mouthfeel of " bitter first ,sweet later ".Nutritious, be conducive to the effects such as human body digestion and beauty treatment.But not storage endurance of olive fresh fruit, easier dehydration after Fruit, brown stain, rotten, adopting several days fruits of rear placement will dehydration shrinkage and old and feeble rotten.Greatly reduce eating quality and commodity value.In recent years, olive plant production development is rapid, because olive fruits skin is thin, adopt rear easy dehydration shrinkage and rot, most fruits are used for being processed into the preserved fruits such as fruit jelly, fresh fruit listing number is less, and on market, the demand of fresh fruit is become to prosperous, and the price of common fresh-keeping olive is 2～3 times of price while gathering.Relevant olive fruits preservation and freshness, has carried out some researchs both at home and abroad.Lin Hetong etc.
[2]point out the suitable harvest in advance of olive fruits than in, late period the storage effect of gathering good, and studied polyethylene film packing, fruit liniment or processed the fresh-keeping effect to olive with derosal and synergistic agent etc.; Someone
[3]think that individual packing has good effect to the maintenance of olive fruits outward appearance and quality.In this simultaneously, olive is one of semi-tropical famous fruit tree, but because its virgin phase is long, tree body is large, is difficult to traditional breeding technique, its kind be hybridized and seed selection, has hindered the improvement of this fruit quality and the development of plant husbandry
[4].PPO is the important enzyme that causes olive Enzymatic browning, Lin Hetong etc.
[5]report the impact of PPO in olive fruits antistaling storing process; Zhan Jiahong
[6]olive fruits PPO characteristic is studied.The people's such as Cai Zongqi research
[7]the PPO inhibitor that shows characteristic has important directive significance for the fresh-keeping anti-brown stain of olive.
Cys (L-Cys) is natural amino acid, and human body is had no side effect, and as a kind of efficient safe polyphenol oxidase enzyme inhibitors, its application in food fresh keeping has obtained some researchs
[8].We once studied the restraining effect of L-Cys to olive PPO, and result of study shows, L-Cys has obvious restraining effect to this enzyme, and its effect can cause the lag time of enzymatic reaction to extend more than 180 times, made stable state enzyme activity decline simultaneously.It causes the inhibitor concentration (IC of enzyme activity decline 50%
50) be 100 μ M.L-Cys is irreversible inhibition to the effect of olive PPO, and it can be used as effective colour protecting agent, suppresses the generation of olive brown product, reaches the freshening effect of olive
[9].Because free L-Cys is easily oxidized, and help the breeding of microorganism, unfavorable as fruit and vegetable fresh-keeping agent.Our seminar finds that the compounds such as many aromatic alcohols (aldehyde, ketone), pmethoxybenzyl alcohol (aldehyde, ketone), furancarbonyl pyrazolone have very strong anti-PPO activity in the PPO inhibitor process of research special efficacy; and there is good anti-microbial activity; the schiff base compounds that we form by this type of material and halfcystine condensation, has biological activity widely.And can be by their antibacterial and anti-PPO activity being improved to introducing different substituting groups on the ring of fragrant heterocyclic aldehydes (ketone)
[10-13].At antibiosis, furancarbonyl pyrazolone halfcystine Schiff's base has stronger anti-microbial activity to staphylococcus aureus, Bacillus subtilus, intestinal bacteria, soft rot of cabbage bacterium, Kidney bean meat or fish vaccine etc.; 2-pyridine benzoyl halfcystine Schiff's base and copper complex thereof also have significant bacteriostatic action.The inhibition of this compounds to PPO and there is not yet report in the applied research in fresh-keeping field.
Reference:
[1] Zhang Fuping, Chen Weihui, Lin Jianxin. the healthy nutritive value of olive and exploitation [J]. food research and development, 2002,23 (4): 48-49
[2] Lin Hetong, Hong Qizheng. the dependency [J] of olive Different Harvesting Time and storage quality energy. Fujian Agricultural Univeristy's journal: natural science edition, 1994,23 (3): 342-345.
[3] Lin Hetong, Hong Qizheng, Liu Yifeng etc. the research [J] of olive liniment storage effect. Fujian fruit tree, 1994 (3): 13-16.
[4] Zhou Xinyue. the olive fruits commerciality fresh-keeping research of room temperature storage [J]. subtropical plant communication, 1994,23 (2): 43-47.
[5] Chen Lian, Lin Hetong, urn bonus etc. the fresh-keeping package technology research [J] of olive fruits. packing and food machinery, 2005,23 (4): 1-3.
[6] Zhan Jiahong. the active inhibition research of PPO and POD [J] in olive fruits. subtropical plant science, 2005,34 (4): 14-16.
[7] Cai Zongqi, Zhang Aijia. olive normal-temperature fresh-keeping gordian technique [J]. southern china fruit tree, 2003,32:4.
[8]Richard-Forget?FC,Goupy?PM,Nicolas?JJ.Cysteine?as?an?inhibitor?of?enzymatic?browning.2.kinetic?studies.J?Agric?Food?Chem,1992,40:2108-2113.
[9] Qiu Longxin, Huang Hao, Chen Qingxi. halfcystine is to the oxidasic restraining effect of olive polyphenol [J]. Food science, 2006,27(4): 37-40.
[10]Ghosh?S,Misra?AK.Bhatia?G.,et?al.Syntheses?and?evaluation?of?glucosyl?aryl?thiosemicarbazide?and?glucosyl?thiosemicarbazone?derivatives?as?antioxidant?and?anti-dyslipidemic?agents.Bioorg.Med.Chem.Lett.,2009,19:386-389.
[11] Li Jinzhou, Zhang Guanglin, Sha Jingquan, etc. synthetic, spectral characterization and the biological activity [J] of. furancarbonyl pyrazolone thiosemicarbazone title complex. spectroscopy and spectroscopic analysis, 2005,25(2): 216-219.
[12] Lu Qin, Wang Guoxiong, the research [J] of .N-pyridine oxide-2-aldehyde thiosemicarbazone cobalt complexes such as Yin Zhanfeng. Chinese Journal of Inorganic Chemistry, 1991,7(1): 65-68.
[13]Halve?AK,Bhashkar?B,Sharma,V,et?al.Synthesis?and?in?vitro?antimicrobial?studies?of?some?new3-[phenyldiazenyl]benzaldehyde?N-phenyl?thiosemicarbazones.J?Enzyme?Inhib?Med?Chem,2008,23:77-81.
Summary of the invention
The object of the present invention is to provide p-ethoxybenzaldehyde Cys Schiff's base and preparation method thereof and application.
The relative molecular weight of described p-ethoxybenzaldehyde Cys Schiff's base (EOBCS) is 253.3174, and its opticity is left-handed, represents with " L ", and its structural formula is as follows:
The preparation method of described p-ethoxybenzaldehyde Cys Schiff's base, comprises the following steps:
1) Cys is added to the water to dissolving, makes the Cys aqueous solution;
2) in the Cys aqueous solution, add dehydrated alcohol, obtain the ethanolic soln of Cys;
3) in Cys ethanolic soln, add oil bath heating after p-ethoxybenzaldehyde and dehydrated alcohol, again after direct suction filtration, rinse and precipitate with dehydrated alcohol, then use ethyl acetate and water recrystallization purifying, obtain white solid product p-ethoxybenzaldehyde Cys Schiff's base, productive rate 75.6%～78.3%.
In step 1), described Cys can adopt 99.99% Cys, and described water can adopt deionization distilled water; Cys in mass ratio: water=1: (0.4～1.8), preferably 1: (1.2～1.4).
In step 2) in, the mass ratio of the described Cys aqueous solution and dehydrated alcohol can be 1: (3.5～6.7), preferably 1: (4.4～5.5).
In step 3), the mass ratio of described Cys ethanolic soln, p-ethoxybenzaldehyde and dehydrated alcohol can be 1: (0.2～0.3): (0.6～0.75); The temperature of described oil bath heating can be 85～120 ℃, and the time of oil bath heating can be 3～3.4h; Rinse precipitation flushable 2～5 times; The mass ratio of described ethyl acetate and water can be (7～9): 1.
Described p-ethoxybenzaldehyde Cys Schiff's base can be applied preparing in olive preservation agent.
Under described p-ethoxybenzaldehyde Cys Schiff's base room temperature, can be dissolved in well in methyl alcohol, methyl-sulphoxide (DMSO) and trifluoroacetic acid (TFA), but dissolution degree is very low in water, dehydrated alcohol, ethyl acetate.Its solvability is an impediment to its application in olive is fresh-keeping, the invention solves its dissolution problems in glycerine, mixed to p-ethoxybenzaldehyde Cys Schiff's base and glycerine, forms emulsion first by a certain percentage.Then add the hot water of approximately 100 ℃, stirring at room temperature certain hour 0.5～1h, p-ethoxybenzaldehyde Cys Schiff's base dissolves gradually.
P-ethoxybenzaldehyde is a kind of weak yellow liquid.P-ethoxybenzaldehyde is mainly used in the synthetic precursor of medicine and intermediate in recent years, for the synthesis of downstream product 4-ethoxy-cinnamic acid, is considered to have certain toxicity and pungency, and its use is restricted.Research shows, p-ethoxybenzaldehyde is also the inhibitor of tyrosine oxidase.But toxicity and the pungency of considering this material, can not be widely used.But show according to research, the aldehyde radical in aldehyde compound plays a crucial role in the process that suppresses microorganism growth, generation toxicity, so the present invention, the aldehyde radical condensation of halfcystine and p-ethoxybenzaldehyde, forms amido bond, reduces the toxicity that aldehyde radical brings.Because the crucial group of halfcystine restraint of tyrosinase is sulfydryl, in synthetic, retain this group, structure and purity by mass spectrum, high resolution mass spec and proton nmr spectra to synthetic are identified, have guaranteed purity and the unicity (seeing Fig. 1～3) of synthetic.Carry out inhibition research by the inhibition kinetic model to external Mushroom Tyrosinase and show, p-ethoxybenzaldehyde Cys Schiff's base is that 0.833 μ M(is shown in Fig. 4 to half inhibiting rate of Mushroom Tyrosinase activity).Half inhibiting rate has embodied the inhibition strength of inhibitor to enzyme, and more the bright inhibition strength of novel is stronger.
Fresh fresh-keeping effect and Ultrastructural research of adopting olive is shown, synthetic p-ethoxybenzaldehyde halfcystine Schiff's base has significant preservation and antisepsis effect, at 10 ℃, under the best olive storage condition of relative humidity 90%, the fresh storage time of adopting olive can be extended to 60 days, and the ultrastructure of relatively intact preservation olive fruits is complete, effectively suppress extremely incident corruption effect in storage process, can suppress well intestinal bacteria, streptococcus aureuses etc. are pathogenic causes rotten bacterium (as Fig. 7), can keep preferably fresh local flavor and the nutritive value of adopting olive.
The security of synthetic compound and high efficiency.Can be seen by Fig. 8, with respect to synthetic substrate p-ethoxybenzaldehyde, using normal human subject liver cell L02 as research object, from cytotoxicity, p-ethoxybenzaldehyde Cys Schiff's base has obviously greatly reduced the cytotoxicity of p-ethoxybenzaldehyde, result shows, it,, on not impact of liver cell growth, does not have liver toxicity.The toxicity that shows p-ethoxybenzaldehyde Cys Schiff's base is very little, can be used for the fresh-keeping effective constituent of olive.
Compared with prior art, tool of the present invention has the following advantages:
1. to be applied to olive fresh-keeping for this preservation agent, has anti-brown stain and antibacterial double effects, and safety non-toxic does not affect again the nutritive value of olive;
2. reaction adopts p-ethoxybenzaldehyde, halfcystine etc., cheap, low production cost, has larger profit margin;
3. can control preferably the brown stain of the olive course of processing, be conducive to the olive processing of food service industry, also be conducive to fresh-cut olive bar, the listing of olive slice simultaneously;
4. p-ethoxybenzaldehyde Cys Schiff's base is characterized in that in test tube, effectively suppressing the vigor of Mushroom Tyrosinase, can effectively suppress the Ultrastructural corrupt dehydration of olive fruits and change, to mankind's normal liver cell L02 nontoxicity;
5. can utilize water, the glycerine solvent as preservation agent, cost is low, safety, and the process for processing that is both applicable to enterprise is also applicable to common peasant household and uses, and has the value that widespread use is promoted.
Accompanying drawing explanation
Fig. 1 is p-ethoxybenzaldehyde Cys Schiff's base low resolution electrospray ionization mass spectrum figure.P-ethoxybenzaldehyde Cys Schiff's base uses Esquire3000plus low resolution electrospray ionization mass spectrum mass spectrograph to test the mass spectrum result obtaining, p-ethoxybenzaldehyde Cys Schiff's base molecular weight is 253, and adding an electronical display quality is 254.6.
Fig. 2 is the high minute mark rate of p-ethoxybenzaldehyde Cys Schiff's base mass spectrum.The mass spectrum result that p-ethoxybenzaldehyde Cys Schiff's base uses the high minute mark rate of Bruker Apex ultra7.0T FT-MS mass spectrograph to detect, p-ethoxybenzaldehyde Cys Schiff's base molecular weight is 253.3174, and adding a mass of the electron is 254.084545.
Fig. 3 is the NMR-H spectrogram of p-ethoxybenzaldehyde Cys Schiff's base.P-ethoxybenzaldehyde Cys Schiff's base uses the nuclear-magnetism evaluation of instrument Bruker600M to the structure of matter altogether, utilizes NMR-H to compose involutory one-tenth p-ethoxybenzaldehyde Cys Schiff's base and carries out Structural Identification.1H?NMR(CD
3OD-d4，TMS，600MHz)：δ(ppm)3.35，5.99(C6H4，4H)，5.43(CH=N)，4.23(CH)，2.02(OC
2H
5，5H)，2.55、2.56(CH
2，2H)。
Fig. 4 is p-ethoxybenzaldehyde Cys Schiff's base inhibition curve to Mushroom Tyrosinase in test tube in the present invention.
Fig. 5 p-ethoxybenzaldehyde Cys Schiff's base is to the fresh treatment effect figure that adopts olive.The effect of p-ethoxybenzaldehyde Cys Schiff's base is fresh adopts olive contrast with water treatment is fresh after adopting olive and storing 60 days, control group is for processing 1min with sterilized water, treatment group is to process 1min with the aqueous glycerin solution of 10mM p-ethoxybenzaldehyde Cys Schiff's base, is 60 days effects of taking pictures of storage in figure.
Fig. 6 is that p-ethoxybenzaldehyde Cys Schiff's base is processed the fresh Electronic Speculum design sketch of adopting olive ultra micro framework.The effect of p-ethoxybenzaldehyde Cys Schiff's base is fresh adopts olive and stores after 60 days and fresh electromicroscopic photograph contrast of adopting olive and control group in the 0th day, Fig. 6 A, 6D are the 0th day olive fruits ultrastructure figure, Fig. 6 B, 6E are the 60th day control group olive ultrastructure, Fig. 6 C, 6F are olive ultrastructure after p-ethoxybenzaldehyde Cys Schiff's base is processed, pericarp magnification is 1000 times, voltage 12000V, pulp magnification is 10000 times, voltage 12000V.
Fig. 7 is the rotten microorganism of restraining effect p-ethoxybenzaldehyde Cys Schiff's base causes to(for) difference.Positive control is Vetstrep 1000u/mL.
Fig. 8 is p-ethoxybenzaldehyde Cys Schiff's base in the present invention, the toxicological study of reaction raw materials p-ethoxybenzaldehyde to people's normal liver cell L02.
Embodiment
By the mode with embodiment, the invention will be further described below, so that those skilled in the art can put into practice the present invention, understands the present invention, can adopt other embodiments, and can make suitable change and not depart from the spirit or scope of the present invention.For fear of for making those skilled in the art can put into practice unnecessary details the present invention, specification sheets may omit some known to those skilled in the art information.Therefore, below describe in detail and should not understand with restrictive meaning.
Following embodiment is convenient to understand better the present invention, but is not used for limiting the scope of the invention.
The each raw material using in following embodiment, except particularly pointing out, all can be by commercially available acquisition.
Embodiment 1: the preparation method of p-ethoxybenzaldehyde Cys Schiff's base:
Cys 100g first adds the stirring of 140mL deionization distilled water that Cys is farthest dissolved, and adds 1500mL dehydrated alcohol, stirs.Add 215mL p-ethoxybenzaldehyde, then add 900mL dehydrated alcohol, stir, heat 121 ℃.After 3h, stopped reaction.Directly suction filtration, with dehydrated alcohol flushing 3 times, 90% sherwood oil aqueous solution recrystallization, obtains white solid product ethoxy-benzaldehyde Cys Schiff's base.
Embodiment 2: p-ethoxybenzaldehyde Cys Schiff's base of the present invention suppresses dynamics research to Mushroom Tyrosinase
The p-ethoxybenzaldehyde Cys Schiff's base obtaining in embodiment 1 is dissolved in to deionization distilled water, makes the solution containing different concns effector.Take 0.5mM L-DOPA as substrate, survey in live body system at the 3mL of 0.05M phosphoric acid buffer (pH6.8), first add the effector of 0.1mL different concns in cuvette, the substrate solution that adds again 2.8mL to be incubated 30 ℃ of waters bath with thermostatic control in advance, then add the 0.05mL Mushroom Tyrosinase aqueous solution, mix at once, the optical density value of measuring wavelength and be 475nm under 30 ℃ of constant temperatures growth straight line in time, try to achieve enzyme activity from the slope of straight line, optical extinction coefficient is pressed ε=3700 (mMcm)
-1calculate.The final concentration of tyrosine oxidase is 3.33 μ g/mL.With the relative surplus vigor pairing effect substrate concentration mapping of enzyme, obtain the concentration-response curve of effector, while being 50% by enzyme relative surplus vigor, the effector concentration that correspondence obtains, tries to achieve the IC of effector
50value (as Fig. 4).
Embodiment 3: p-ethoxybenzaldehyde Cys Schiff's base of the present invention is fresh-keeping to olive
According to mentioning way in explanation, the p-ethoxybenzaldehyde preparation aqueous glycerin solution that embodiment 1 is obtained, final concentration is 10mM, will gather olive the same day and get 50 and be placed in gained aqueous glycerin solution and soak 1min, wipes dry, control group uses sterilizing deionization distilled water to process equally, rear pack is stored in growth cabinet (10 ℃, relative humidity 90%), within every 5 days, changes a reservoir bag, within 60 days, stop storing, take pictures as shown in Figure 5.The 0th day olive deposits-80 ℃ in and stops preserving, and the 60th day olive control group and drug treating group are cut respectively 1mm
3fritter and mda are fixed 4～6h, and 1xPBS rinses three times, embedding, and section, metal spraying, Bruker JEM2100HC12000V voltage sweep Electronic Speculum is taken, and observes, as shown in Figure 5.Result shows, the p-ethoxybenzaldehyde L halfcystine Schiff's base in the present invention can effectively keep fresh freshness of adopting olive, prevents olive brown stain corruption, effectively protects olive fruits Ultrastructural complete, keeps freshness and the nutritive value of olive.
Embodiment 4: the toxicological study to people's normal liver cell L02 cell of p-ethoxybenzaldehyde Cys Schiff's base of the present invention
With DMEM HighGlucose substratum (containing 10% viviparous calf serum, penicillin 100U/mL, Streptomycin sulphate 100 μ g/mL), at CO
237 ℃, CO in incubator
2=5% and the condition of saturated humidity under culturing cell.Treat that Growth of Cells is to nearly fusion state, after 0.25% tryptic digestion, collecting and adjust cell concn is 10
4/ mL is in 96 porocyte culture plates.People's normal liver cell L02 single cell suspension that every hole adds 200 μ L, spends the night.After cell attachment, discard former substratum, add respectively p-ethoxybenzaldehyde Cys Schiff's base that the embodiment of the present invention 1 containing 10,30,50 and 100 μ M obtains and the DMEM HighGlucose substratum 200 μ L of p-ethoxybenzaldehyde.After continuing to cultivate 48h, abandon nutrient solution.4h before finishing, with PBS damping fluid (137mM NaCl, 2.7mM KCl, the 10mM Na of pH7.4
2hPO
4, 2mM KH
2pO
4) wash 2 times, every hole adds 0.5mg/mL MTT and the fresh DMEM HighGlucose nutrient solution of 180 μ L of 20 μ L, at CO
2in incubator at 37 ℃, CO
2=5% and the condition of saturated humidity under after culturing cell 4h, abandon supernatant liquor.Every hole adds 200 μ L DMSO, and under 37 ℃ of conditions, concussion 10min, dissolves bluish voilet Jie Jing formazan completely.Measure 570nm absorbance value by microplate reader immediately.3 repetitions are established in each concentration processing, average.Same passage cell is all got in each experiment.Result as shown in Figure 6.
As shown in Figure 7: 10, the p-ethoxybenzaldehyde Cys Schiff's base of 30,50 and 100 μ M does not have a significant effect to the propagation of people's normal liver cell L02, and no cytotoxicity or hypotoxicity are described; And p-ethoxybenzaldehyde has restraining effect to the increment of people's normal liver cell L02, cytotoxicity is described.
Claims (10)
1. p-ethoxybenzaldehyde Cys Schiff's base, is characterized in that its relative molecular weight is 253.3174, and its opticity is left-handed, represents with " L ", and its structural formula is as follows:
2. the preparation method of p-ethoxybenzaldehyde Cys Schiff's base as claimed in claim 1, is characterized in that comprising the following steps:
1) Cys is added to the water to dissolving, makes the Cys aqueous solution;
2) in the Cys aqueous solution, add dehydrated alcohol, obtain the ethanolic soln of Cys;
3) in Cys ethanolic soln, add oil bath heating after p-ethoxybenzaldehyde and dehydrated alcohol, again after direct suction filtration, rinse and precipitate with dehydrated alcohol, then use ethyl acetate and water recrystallization purifying, obtain white solid product p-ethoxybenzaldehyde Cys Schiff's base.
3. the preparation method of p-ethoxybenzaldehyde Cys Schiff's base as claimed in claim 2, is characterized in that in step 1), and described Cys adopts 99.99% Cys, and described water can adopt deionization distilled water.
4. the preparation method of p-ethoxybenzaldehyde Cys Schiff's base as claimed in claim 2, is characterized in that in step 1), in mass ratio Cys: water=1: (0.4～1.8).
5. the preparation method of p-ethoxybenzaldehyde Cys Schiff's base as claimed in claim 2, is characterized in that in step 2) in, the mass ratio of the described Cys aqueous solution and dehydrated alcohol is 1: (3.5～6.7).
6. the preparation method of p-ethoxybenzaldehyde Cys Schiff's base as claimed in claim 2, is characterized in that in step 1), in mass ratio Cys: water=1: (1.2～1.4); In step 2) in, the mass ratio of the described Cys aqueous solution and dehydrated alcohol is 1: (4.4～5.5).
7. the preparation method of p-ethoxybenzaldehyde Cys Schiff's base as claimed in claim 2, it is characterized in that in step 3), the mass ratio of described Cys ethanolic soln, p-ethoxybenzaldehyde and dehydrated alcohol is 1: (0.2～0.3): (0.6～0.75).
8. the preparation method of p-ethoxybenzaldehyde Cys Schiff's base as claimed in claim 2, is characterized in that in step 3), and the temperature of described oil bath heating is 85～120 ℃, and the time of oil bath heating is 3～3.4h; Rinse precipitation flushable 2～5 times.
9. the preparation method of p-ethoxybenzaldehyde Cys Schiff's base as claimed in claim 2, is characterized in that in step 3), the mass ratio of described ethyl acetate and water is (7～9): 1.
As claimed in claim 1 p-ethoxybenzaldehyde Cys Schiff's base in the application of preparing in olive preservation agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410148587.0A CN103880724A (en) | 2014-04-14 | 2014-04-14 | Ethoxybenzaldehyde L-cysteine schiff base as well as preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410148587.0A CN103880724A (en) | 2014-04-14 | 2014-04-14 | Ethoxybenzaldehyde L-cysteine schiff base as well as preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103880724A true CN103880724A (en) | 2014-06-25 |
Family
ID=50949894
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410148587.0A Pending CN103880724A (en) | 2014-04-14 | 2014-04-14 | Ethoxybenzaldehyde L-cysteine schiff base as well as preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103880724A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116440949A (en) * | 2023-02-02 | 2023-07-18 | 东南大学 | A cluster enzyme loaded with Schiff base and its preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6407071B1 (en) * | 1998-06-04 | 2002-06-18 | Co-Enzyme Technology Ltd. | Method and composition for treating malignant cells |
| CN1907966A (en) * | 2006-08-21 | 2007-02-07 | 厦门大学 | 2-(benzylideneamino)-3-mercaptopropanoic acid, preparation method and application thereof in cosmetics |
| EP2301581A1 (en) * | 2001-04-03 | 2011-03-30 | Immunomedics, Inc. | Production and use of novel peptide-based agents for use with B1-specific antibodies |
-
2014
- 2014-04-14 CN CN201410148587.0A patent/CN103880724A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6407071B1 (en) * | 1998-06-04 | 2002-06-18 | Co-Enzyme Technology Ltd. | Method and composition for treating malignant cells |
| EP2301581A1 (en) * | 2001-04-03 | 2011-03-30 | Immunomedics, Inc. | Production and use of novel peptide-based agents for use with B1-specific antibodies |
| CN1907966A (en) * | 2006-08-21 | 2007-02-07 | 厦门大学 | 2-(benzylideneamino)-3-mercaptopropanoic acid, preparation method and application thereof in cosmetics |
Non-Patent Citations (2)
| Title |
|---|
| 宋康康: "抑制剂对酪氨酸酶的效应及其对黑色素生成调控的研究", 《中国博士学位论文全文数据库 基础科学辑》 * |
| 陈清西 等: "酪氨酸酶抑制剂的研究进展", 《厦门大学学报(自然科学版)》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116440949A (en) * | 2023-02-02 | 2023-07-18 | 东南大学 | A cluster enzyme loaded with Schiff base and its preparation method and application |
| CN116440949B (en) * | 2023-02-02 | 2024-10-01 | 东南大学 | Schiff base-loaded cluster enzyme and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100892596B1 (en) | Biphenyl Diol Derivatives and Compositions Comprising the Same as Active Ingredients | |
| KR101997893B1 (en) | Method of increase the bioactive effectiveness of sprout ginseng | |
| KR101496359B1 (en) | Method for producing breathing fermented solution of wild plants | |
| KR101432584B1 (en) | Method for steamed and fermented Codonopsis lanceolata for boosting biological activity | |
| KR102428987B1 (en) | Composition Containing Extracts of Camellia sinensis | |
| Ranjan et al. | Enhancement of Syzygium cumini (Indian jamun) active constituents by ultra-violet (UV) irradiation method | |
| KR20110085758A (en) | Extract containing sprouted barley-derived polyphenol-based compound and preparation method thereof | |
| Yashaswini et al. | Noni: a new medicinal plant for the tropics | |
| KR20180052823A (en) | Cosmetic compositions and wet tissue solution containing natural preservatives | |
| KR20160115311A (en) | Antibacterial and antifungal composition comprising plant extracts | |
| KR20150064314A (en) | Cosmetic Composition Comprising Mangifera indica L. Extract, Passiflora edulis Sims Extract, Hylocereus undatus (Haw.) Britt. and Rose Extract, Actinidia chinensis Planch. Extract and Annona Squamosa Extract | |
| KR101248056B1 (en) | Cosmetic composition for deoderizing odl men smell by using orental natural materials | |
| KR101664025B1 (en) | Cosmetic composition containing natural herb extracts | |
| CN105053169B (en) | A kind of edibility strawberry compound antistaling agent and preparation method thereof | |
| KR20190075382A (en) | High concentrate for beverage containing black raspberry, plantaginis asiatica l., schizandra chinensis, lycii fructus and torilis japonica decandolle and the high concentrate for beverage prepared from the same | |
| KR102059392B1 (en) | Antimicrobial and Antifungal Composition Containing Clove, Hibiscus, and Coconut Extract Complex as Active Ingredient | |
| KR20210025930A (en) | Cosmetic composition comprising mangifera indica irwin seed extract | |
| BRPI0714848B1 (en) | USING A 5-AMINOLEVULINIC ACID DERIVATIVE AND METHOD TO INCREASE POLYPHENOL CONTENT IN A PLANT | |
| CN103880724A (en) | Ethoxybenzaldehyde L-cysteine schiff base as well as preparation method and application thereof | |
| KR101875738B1 (en) | extraction method for a lacquer liquid of lacquer tree's a leaf and seeds | |
| KR101512811B1 (en) | Cosmetic Composition Comprising Reynoutria japonica for. elata Extract for Skin Whitening | |
| Patel et al. | Screening of antibacterial activity of some underutilized fruits of Sapotaceae | |
| Allai et al. | Black Currant | |
| KR101863117B1 (en) | Composition comprising Androsace umbellate extract, Vaccinium oldhami extract, and Deutzia crenata extract | |
| KR100567620B1 (en) | Manufacturing Method of Functional Camellia Tea |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140625 |