WO2017068548A1 - Novel amino acid/peptide-zinc hybrid nanomaterials and process of preparation thereof - Google Patents
Novel amino acid/peptide-zinc hybrid nanomaterials and process of preparation thereof Download PDFInfo
- Publication number
- WO2017068548A1 WO2017068548A1 PCT/IB2016/056356 IB2016056356W WO2017068548A1 WO 2017068548 A1 WO2017068548 A1 WO 2017068548A1 IB 2016056356 W IB2016056356 W IB 2016056356W WO 2017068548 A1 WO2017068548 A1 WO 2017068548A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- amino acid
- hybrid nano
- zinc
- hybrid
- synthesis
- Prior art date
Links
- 150000001413 amino acids Chemical class 0.000 title claims abstract description 94
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000011701 zinc Substances 0.000 title claims description 30
- 229910052725 zinc Inorganic materials 0.000 title claims description 29
- 230000008569 process Effects 0.000 title abstract description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 58
- 108090000765 processed proteins & peptides Proteins 0.000 claims abstract description 42
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims abstract description 37
- 229940007718 zinc hydroxide Drugs 0.000 claims abstract description 34
- 239000011787 zinc oxide Substances 0.000 claims abstract description 31
- 239000013078 crystal Substances 0.000 claims abstract description 17
- 229940024606 amino acid Drugs 0.000 claims description 94
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 75
- 230000015572 biosynthetic process Effects 0.000 claims description 30
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 27
- 238000003786 synthesis reaction Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 claims description 17
- 239000004474 valine Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical group [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 13
- 239000004246 zinc acetate Substances 0.000 claims description 13
- KZSNJWFQEVHDMF-UHFFFAOYSA-N Valine Natural products CC(C)C(N)C(O)=O KZSNJWFQEVHDMF-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000011541 reaction mixture Substances 0.000 claims description 8
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 7
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 claims description 7
- 229920001184 polypeptide Polymers 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000000527 sonication Methods 0.000 claims description 7
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 7
- 239000004472 Lysine Substances 0.000 claims description 6
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 5
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 102000004196 processed proteins & peptides Human genes 0.000 claims description 5
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 claims description 5
- 239000004471 Glycine Substances 0.000 claims description 4
- AGPKZVBTJJNPAG-WHFBIAKZSA-N L-isoleucine Chemical compound CC[C@H](C)[C@H](N)C(O)=O AGPKZVBTJJNPAG-WHFBIAKZSA-N 0.000 claims description 4
- ROHFNLRQFUQHCH-YFKPBYRVSA-N L-leucine Chemical compound CC(C)C[C@H](N)C(O)=O ROHFNLRQFUQHCH-YFKPBYRVSA-N 0.000 claims description 4
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 claims description 4
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 claims description 4
- AYFVYJQAPQTCCC-GBXIJSLDSA-N L-threonine Chemical compound C[C@@H](O)[C@H](N)C(O)=O AYFVYJQAPQTCCC-GBXIJSLDSA-N 0.000 claims description 4
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 claims description 4
- ROHFNLRQFUQHCH-UHFFFAOYSA-N Leucine Natural products CC(C)CC(N)C(O)=O ROHFNLRQFUQHCH-UHFFFAOYSA-N 0.000 claims description 4
- AYFVYJQAPQTCCC-UHFFFAOYSA-N Threonine Natural products CC(O)C(N)C(O)=O AYFVYJQAPQTCCC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004473 Threonine Substances 0.000 claims description 4
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 229960000310 isoleucine Drugs 0.000 claims description 4
- AGPKZVBTJJNPAG-UHFFFAOYSA-N isoleucine Natural products CCC(C)C(N)C(O)=O AGPKZVBTJJNPAG-UHFFFAOYSA-N 0.000 claims description 4
- 229930182817 methionine Natural products 0.000 claims description 4
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000004475 Arginine Substances 0.000 claims description 3
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 claims description 3
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 claims description 3
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims 2
- 238000001914 filtration Methods 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 27
- 229910052751 metal Inorganic materials 0.000 abstract description 17
- 239000002184 metal Substances 0.000 abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- 241001465754 Metazoa Species 0.000 abstract description 4
- 235000016709 nutrition Nutrition 0.000 abstract description 4
- 235000001014 amino acid Nutrition 0.000 description 75
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 23
- 229960001296 zinc oxide Drugs 0.000 description 23
- 235000014692 zinc oxide Nutrition 0.000 description 22
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 20
- 239000002057 nanoflower Substances 0.000 description 18
- 239000011159 matrix material Substances 0.000 description 15
- 238000002441 X-ray diffraction Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 239000012153 distilled water Substances 0.000 description 12
- 229960004295 valine Drugs 0.000 description 12
- -1 L-Tyrosine-zinc hydroxide Chemical compound 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 description 10
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 10
- 238000001878 scanning electron micrograph Methods 0.000 description 9
- 229960001153 serine Drugs 0.000 description 9
- 229960004441 tyrosine Drugs 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000002070 nanowire Substances 0.000 description 6
- 235000018102 proteins Nutrition 0.000 description 6
- 102000004169 proteins and genes Human genes 0.000 description 6
- 108090000623 proteins and genes Proteins 0.000 description 6
- 238000002525 ultrasonication Methods 0.000 description 6
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 239000002071 nanotube Substances 0.000 description 5
- 229960002429 proline Drugs 0.000 description 5
- MTCFGRXMJLQNBG-UWTATZPHSA-N D-Serine Chemical compound OC[C@@H](N)C(O)=O MTCFGRXMJLQNBG-UWTATZPHSA-N 0.000 description 4
- 229930195711 D-Serine Natural products 0.000 description 4
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910010272 inorganic material Inorganic materials 0.000 description 4
- 239000011147 inorganic material Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 235000018977 lysine Nutrition 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- KZSNJWFQEVHDMF-SCSAIBSYSA-N D-valine Chemical compound CC(C)[C@@H](N)C(O)=O KZSNJWFQEVHDMF-SCSAIBSYSA-N 0.000 description 3
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000005842 biochemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 230000005291 magnetic effect Effects 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000002114 nanocomposite Substances 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 229930182831 D-valine Natural products 0.000 description 2
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 2
- 229930182821 L-proline Natural products 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 235000013922 glutamic acid Nutrition 0.000 description 2
- 239000004220 glutamic acid Substances 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910001463 metal phosphate Inorganic materials 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000008520 organization Effects 0.000 description 2
- 230000005298 paramagnetic effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- QIVKNPAIBQIBIQ-ACCHAWBCSA-N C([C@@H](C(=O)O)N)SSC[C@@H](C(=O)O)N.N[C@@H](CC1=CC=C(C=C1)O)C(=O)O Chemical compound C([C@@H](C(=O)O)N)SSC[C@@H](C(=O)O)N.N[C@@H](CC1=CC=C(C=C1)O)C(=O)O QIVKNPAIBQIBIQ-ACCHAWBCSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 150000008574 D-amino acids Chemical class 0.000 description 1
- 102000052510 DNA-Binding Proteins Human genes 0.000 description 1
- 108700020911 DNA-Binding Proteins Proteins 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 1
- LEVWYRKDKASIDU-IMJSIDKUSA-N L-cystine Chemical compound [O-]C(=O)[C@@H]([NH3+])CSSC[C@H]([NH3+])C([O-])=O LEVWYRKDKASIDU-IMJSIDKUSA-N 0.000 description 1
- 235000019393 L-cystine Nutrition 0.000 description 1
- 239000004158 L-cystine Substances 0.000 description 1
- 102000010750 Metalloproteins Human genes 0.000 description 1
- 108010063312 Metalloproteins Proteins 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 102000015636 Oligopeptides Human genes 0.000 description 1
- 108010038807 Oligopeptides Proteins 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000010976 amide bond formation reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000003592 biomimetic effect Effects 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910000153 copper(II) phosphate Inorganic materials 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
- 229960002433 cysteine Drugs 0.000 description 1
- 229960003067 cystine Drugs 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000037213 diet Effects 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- 239000003797 essential amino acid Substances 0.000 description 1
- 235000020776 essential amino acid Nutrition 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 210000003736 gastrointestinal content Anatomy 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 238000002595 magnetic resonance imaging Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- FEMOMIGRRWSMCU-UHFFFAOYSA-N ninhydrin Chemical compound C1=CC=C2C(=O)C(O)(O)C(=O)C2=C1 FEMOMIGRRWSMCU-UHFFFAOYSA-N 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 230000036642 wellbeing Effects 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
- 235000009529 zinc sulphate Nutrition 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/10—Organic substances
- A23K20/142—Amino acids; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/10—Organic substances
- A23K20/142—Amino acids; Derivatives thereof
- A23K20/147—Polymeric derivatives, e.g. peptides or proteins
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/20—Inorganic substances, e.g. oligoelements
- A23K20/30—Oligoelements
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/761—Biomolecules or bio-macromolecules, e.g. proteins, chlorophyl, lipids or enzymes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Definitions
- the present invention relates to a novel compound of zinc with amino acid or peptide in nanomaterials form. More preferably, the present invention further discloses the different type of hybrid nanomaterials comprising at least one amino acids and zinc oxide/hydroxide.
- the said nanomaterials are of definite crystal morphology.
- the process provided by the invention has the advantage of providing controlled crystal morphology over uniform size.
- the said complex have application in various industry more focused pharmaceutical area due to absorbability of the complex and the ability of the complex to participate in biochemical reactions.
- the safety of metal-amino acid/peptide complexes is enhanced by the use of natural amino acids and by improving its bioavailability to minimize the amount of metal added to the feed to meet the nutritional requirements of animals.
- These hybrid materials may be further use in photodiodes and solar cells.
- Nano-technology has been widely used in various disciplines such as optical, electrical, magnetic and catalytic, and many other fieldswith a special appearance of complex new structure, it thus provide more opportunities to explore their new properties.
- researchers are working on nanomaterials composition, structure, shape, size and arrangement and other controls to be prepared in line with the intended function of various nanomaterials.
- Organic-inorganic hybrid nanomaterial is the second single-component materials, composites and functionally graded materials after the 4th generation of new material, because of its constant matching the structure, scale, especially after reaching the nanoscale range to achieve a material properties within the scope of molecules, atoms and other controllable has become one of the most promising research directions in material science.
- the inorganic-organic hybrid new material and its unique properties are widely used in the photodiodes and solar cells and other high-tech devices, thus leads to great deal of attention.
- the inorganic and organic materials together form a new type of special structure of an organic inorganic hybrid nanomaterial, it is possible to enhance the light, electric and magnetic properties of an inorganic material, and to improve the rigidity and thermal stability of the inorganic material, and also can improves morphological controllability as well as having excellent properties. Due to a combination of inorganic materials such respective advantages of organic materials, with high stability and rigidity, has many excellent properties in terms of mechanical, optical, thermal, electromagnetic and biology, and thus become a hot material science.
- Amino acids are the basic constituents of life. They are biologically important organic compounds. Proteinogenic and non-proteinogenic amino acids are important in body functions, catalysis and as drugs. Decoration of nanop article surface by various proteins and amino acid has been proved as an effective strategy to improve biocompatibility of nanoparticles or functional nanoparticles.
- the reports on synthesis of amino acid-metal nanocomposite materials are available only for L-cystein-CuO hierarchical structure and L-Proline immobilized on ZnS nanoparticles. Also various organic material like protein, DNA, polysaccharides, collagen, chitosan, silica and polymers are combined with metals is the well known research area in organic-inorganic hybrid nanomaterials.
- WO2013003836 discloses a hybrid materials and nanocomposite materials comprising metal precursor compounds embedded in a carbon matrix. A method is reported for creating functional organic-inorganic hybrid materials by copolymerization of organic molecules and inorganic compounds.
- Patent publication no. WO 2007124131 provides a contrast agent for magnetic resonance imaging (MRI) comprising a hybrid nanoparticle, said hybrid nanoparticle comprising: a polymeric matrix material; and a plurality of coordination complexes, each coordination complex comprising a functionalized chelating group and a paramagnetic metal ion, wherein the paramagnetic metal ion comprises an element selected from the group consisting of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, molybdenum, ruthenium, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, and ytterbium.
- MRI magnetic resonance imaging
- US patent No US 8,759,245 discloses a method for preparing iron -containing porous organic-inorganic hybrid materials where the organic compound ligand is bonded to a central metal.
- European patent No EP2089313A2 provides Metal -polymer hybrid nanomaterials comprise nanotubes or nanowires and metal layers formed on the inner or outer surfaces of the nanotubes or the outer surfaces of the nanowires.
- the nanotubes or nanowires include a light- emitting ⁇ -conjugated polymer and the metal layers are composed of a metal whose surface plasmon energy level is close to the energy band gap of the nanotubes or nanowires.
- a flower-shaped nano-materials made of metal phosphate and protein hybrid formation and said metal phosphate is ⁇ 3 ( ⁇ 0 4 ) 2 , Zn 3 (P0 4 ) 2 or Cu 3 (P0 4 )2.
- the present inventors have surprisingly invented the novel organic-inorganic hybrid nanomaterials i.e. amino acid/peptide doped with zinc hydroxide/oxide and method of synthesis thereof.
- novel amino acid-zinc oxide/ hydroxide hybrid nanoflowers comprising at least one amino acid and/or mixture thereof as organic moiety and inorganic moiety are of zincoxide/ hydroxide.
- US8,741,375 B2 discloses a mixed amino acid metal salt complex of the amino acids, lysine and glutamic acid associated with trace metals selected from the group consisting of iron, manganese, copper and zinc to provide highly bioavailable sources of the iron, manganese, copper and zinc and different amino acid transport pathways of lysine and glutamic acid.
- US5, 698,724 A discloses the method and composition involves preparing a high yield of a metal amino acid complex, visible as a source of highly bioavailable transition metal ions, highly bioavailable essential amino acid for a livestock animal is disclosed.
- CN 101905328 provide a method for preparing watersolubleAulOnanocluster molecules.
- the invention discloses a method for preparing watersolubleAulO nanocluster molecules through a biomolecule induction onestepreaction.
- the method comprises the following steps of: 1) dissolving histidine in water and stirring the solution to obtain 0.0033 to 0.2 M aqueous solution of the histidine; 2) dissolvingchloroauric acid in the water and stirring the solution to obtain 10 mM aqueous solution of the chloroauric acid; and 3) adding 3 mL of the 0.0033 to 0.2 Maqueous solution of the histidine into 1 mL of the 10 mM aqueous solution of thechloroauric acid, adjusting the pH value of the solution to be between 2 and 11, fully mixing and standing for 1 hour to obtain the watersolubleAulO nanocluster molecules.
- a watersolublenanoclustersAulO obtained by the method emits a bluegreenfluorescent light and the fluorescence quantum
- the inventors have also developed a simple method to synthesis said hybrid nanomaterials by ultrasonication which is offering many advantages like simple, green, economically effective, non-toxic with less reaction time. As the need of environmental protection chemicals used in this preparation is non-toxic and inexpensive.
- the present inventors has surprisingly found the process for novel zinc peptide nanomaterialsusing pure amino acid as the starting reactant to prepare themetal peptide complex which exhibit complete enantioselectiveself assembly.
- the present invention offers a solution by enantioselectivesupramolecularself organization of unactivated amino acids with Zinc.
- current invention shows enantioselectiveself organization of zinc peptide nanomaterials from single or multiple amino acids in water at desired temperature without using any coupling reagent or activated amino acid.
- the said complex have application in pharmaceutical area due to absorbability of the complex and the ability of the complex to participate in biochemical reactions.
- the safety of metal-peptide complexes is enhanced by the use of natural amino acids and by improving its bioavailability to minimize the amount of metal added to the feed to meet the nutritional requirements ofanimals.
- the main objective of present invention is to provide novel nanomaterials of amino acid- zinc oxide/ hydroxide hybrid complex.
- the primary objective of the present invention is to provide a novel zinc oxide peptide complexnanomaterials.
- the main objective of present invention is to provide novel method for preparation of nanomaterials of amino acid-zinc hydroxide hybrid complex.
- a further objective of the present invention is to provide aprocess for preparation of zinc oxide peptide complex.
- the further object of the invention is to provide amino acid-zinc hydroxide hybrid nanomaterials with size ranges from 30 nm to 6 ⁇ .
- Another object of the invention is to develop a novel method for preparation of amino acid-zinc hydroxide nanomaterials using low cost and easily available, less toxic, inexpensive chemicals. • A further objective of the invention is to provide a process for synthesis of enenatioselective zinc oxide peptide complexnanomaterials.
- Another objective of the invention is to provide a simple self assembling process of peptide from precursor of amino acids at desired temperature.
- ZO is selected from Zinc oxide, Zinc Hydroxide
- R is polypeptide, amino acid
- the diameter of said hybrid nano - material is from 30 nm to 6000 nm having controlled crystal morphology.
- the present invention relates to a novel amino acid-zinc oxide/ hydroxide hybrid nano materials and a preparation method thereof. More preferably, the present invention is providing a novel organic-inorganic nano-sized hybrid material wherein one amino acid or more than one amino acid is coupled with zinc hydroxide. Morphology of final amino acid-zinc hydroxide hybrid nanomaterials is depending upon the type of amino acid present in complex.
- the present invention also relates to process for synthesis of said novel hybrid nanomaterials, which controls the overall crystal morphology of hybrid nanomaterials. In case of L-tyrosine the formation of hybrid nanoflowers has controlled uniform size ranging from 500 nm to 600 nm, with uniformly growing slices of petals or needles ranging from 40 nm to 60 nm.
- the said peptide bond isself assembled from the number of amino acids at the time of synthesis of complex.
- FIGURE1 Depict the XRD comparisons of (a) pure amino acid (i.e., L-Tyrosine) (b) pure Zn(OH) 2 (c) L-Tyrosine- Zn(OH) 2 hybrid nanoflowers (d) L-Tyrosine (blue) and Zn(OH) 2 (red).
- FIGURE2 Depict the FEG-SEM images of L-Tyrosine-zinc hydroxide hybrid nanoflowers obtained in example 1.
- FIGURE3 Depict the FT-IR Spectra of L-Tyrosine-zinc hydroxide hybrid nanoflowers obtained in example 1.
- FIGURE4 Depict the EDS spectrum of amino acid-zinc hydroxide hybrid nanoflowers obtained in example 1.
- FIGURE5 Depict the FEG-SEM images of Zinc Hydroxide -Valine hydride nano- material obtained in example 2.
- FIGURE6 Depict the FEG-SEM images of Zinc Hydroxide-Cystiene hydride nano- material obtained in example 3.
- FIGURE7 Depict the FEG-SEM images of Zinc Hydroxide-Proline hydride nano- material obtained in example 4.
- FIGURE8 Depict the FEG-SEM images of Zinc oxide-Tyrosine/Cystiene hydride nano- material obtained in example 5.
- FIGURE 9 Depict the SEM images of zinc oxide peptide wherein nanoflowers like structures observe in NaOH matrix when amino acid is L- Valine.
- FIGURE 10 Depict the SEM images of zincoxide peptide wherein nanoflower were observed in NaOH matrix when amino acid isD-Valine.
- FIGURE ll Depict the SEM images ofzincoxide peptide wherein dense nanoflower crystals were observed in NaOH matrix when amino acid is L- Valine and D-Valine is in 0.5:0.5 ratio.
- FIGURE 12 Depict FT-IR spectras Pattern of different complex.
- FIGURE13 Depict X-ray Diffraction Pattern of different complex.
- FIGURE 14 Depict the SEM images of zinc oxide peptide wherein agglomerated nanoflower were observed in NaOH matrix when amino acid isL-Serine.
- FIGURE 15 Depict the SEM images of zinc peptide wherein agglomeratednanoflower and unorganized crystals were observed in NaOH matrix when amino acid isD-Serine .
- FIGURE16 Depict the SEM images of zinc oxide peptide wherein
- agglomeratednanoflowercrystals were observed in NaOH matrix when amino acid isL- Serine and D-Serine is in raotio of 0.5:0.5.
- ZO is selected from Zinc oxide, Zinc Hydroxide
- R is polypeptide, amino acid
- the diameter of said hybrid nano - material is from 30 nm to 6000 nm having controlled crystal morphology.
- the present invention involves the design, synthesis and evaluation of novel safe and effective zinc oxide/hydroxidepeptide/amino acid nanomaterials. More preferably, the present invention provides anenantioselective compounds of zinc oxide peptide nanomaterials and zinc hydroxide aminoacid nanomaterial.
- anenantioselective compounds of zinc oxide peptide nanomaterials and zinc hydroxide aminoacid nanomaterial includehomochirality, cooperativetyeffect.Stability of the complex at the pHs of the GI contents, absorbability of the complex and the ability of the complex to participate in biochemical reactions.
- the safety of metal-peptide complexes is enhanced by the use of natural amino acids and by improving its bioavailability to minimize the amount of metal added to the feed to meet the nutritional requirements ofanimals.
- the present invention is providing novel amino acid- zinc hydroxide hybrid complex nanomaterial.
- the said hybrid nanomaterials comprises of at least one amino acid forming a hybrid complex with inorganic zinc hydroxide in the molar ratio of 0.3: 1 to 2: 1; wherein the crystal diameter of said hybrid nano-material is in the of 30 nm to 6 ⁇ and having control crystal morphology.
- the present invention provides a method for preparing amino acid-zinc hydroxide hybrid nanomaterial having a relatively small nano particle size and control crystal morphology through an environmentally friendly method.
- the observed crystal morphology is flower shape, bi-pyramidal shape, wulfenite shape, needle shape and rod shape of nanomaterial and microcrystals.
- the said amino acids are selected from a group of non-polar aliphatic side group's, aromatic side groups, polar uncharged side groups and positively charged side groups amino acid.
- the selected amino acids are Valine, aromatic side group's amino acid (Tyrosine), polar uncharged side groups amino acid (Proline) and positively charged side groups amino acid (histidene).
- the present invention is not limited to the amino acids disclosed herein. Rather, any suitable amino acid can be used to prepare the hybrid material in accordance with the various methods disclosed herein.
- amino acid are selected from proteinogenic amino acids and non- proteinogenic amino acids, a tyrosine, cysteine, valine, proline, histidene or mixture thereof.
- second embodiment of present invention provides a method of preparation of amino acid- zinc hydroxide hybrid complex comprising steps of: a. Preparation of reaction mixture containing zinc precursor and at least one amino acid in presence of reagent, zinc precursor is selected from zinc acetate.
- the said reagent is selected from sodium hydroxide, Potassium hydroxide and amino acid is selected from a group of non-polar aliphatic side groups amino acid, aromatic side groups amino acid, polar uncharged side groups amino acid and positively charged side groups amino acid.
- b. Treating the said reaction mixture with ultrasonic frequencies using probe sonicator. The ultrasonic frequencies are in the range from 20 kHz to 40 kHz.
- step b) Washing of product obtained in step b) with solvent like ethanol and water or their mixture d. Drying of sample is done at temperature between 20 °C to 70 °C for a time period of 10 min to 2 hr.
- the nanomaterial having a crystal diameter of 30 nm to 6 ⁇ is formed at ultrasonic range of 20 kHz to 40 kHz and 40% amplitude performed for 5 sec. on/off mode,
- solvent used to prepare the precursor solution and amino acid solution is selected from water only.
- the synthesis of various amino acids-zinc hydroxide hybrid complexes using combination of one or more amino acids can be done using this method.
- the presence of each amino acid in the nanomaterials was also confirmed by ninhydrin test for amino acid with change in color.
- the process can be applicable to all type of amino acids z.e.proteinogenic amino acids and non- proteinogenic amino acids preferably amino acids such as Tyrosine, Cystiene, Valine, Proline, Histidene.
- the process is suitably controls the morphology of nanomaterials.
- shape of resulting amino acid- zinc hydroxide hybrid complex nanomaterials is nanoflowers, however shape and size of amino acid-zinc hydroxide hybrid complex nanomaterials changes with changes in amino acids.
- Morphology of amino acid-zinc hydroxide hybrid nanoflowers with L-Tyrosine is controlled over uniform size ranging from 500 nm to 600 nm, with uniformly growing slices of petals ranging from 40 nm to 60 nm.
- the synthesized amino acid-zinc hydroxide hybrid complex nanomaterial comprises of formation of peptide bond linkage with one or two amino acids.
- the solvent used is any volatile alcohols like methanol, ethanol, propanol, isopropyl alcohol with or without mixture of water.
- the said peptide bond isself assembled from the number of amino acids at the time of synthesis of complex.
- the parent amino acids are selected from but not limited toarginine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, threonine, tryptophan valine, glycine, etc and mixture thereof.
- the present invention alsoprovides a process for enantioselective control over structure and physicochemical properties of zinc peptide nanomaterials.Andvisual discrimination in hybrid nanostructures with enantioselective L- and D-amino acid through the self assembly during peptide bond formation.
- the chiroselective zinc peptide nanostructures is precipitated out by the addition of zinc acetate, amino acid with sodium hydroxidein alkalinewater. Further drain out a aqueous layer and drying out precipitate at room temperature (31°C) for more than 48 hr.
- Zinc oxide peptide nanostructure is prepared by adding zinc precussor with amino acid and solvent. This solution is stirred till complete dissolution is done. Alkali is added with stirring and precipitate is obtain. Heating is done later washing and filteration is doneand final product is obtained.
- Zinc precussor is not limiting to zinc acetate, zinc sulphate etc.
- the zinc precursor is preferably selected form zinc acetate.
- the solvent used in the process is water, alcohol or combination thereof.
- Alkali used could be sodium hydroxide, potassium hydroxide.
- Alkali used could be sodium hydroxide, potassium hydroxide.
- Example 1 Method of Preparation: The mixture of zinc acetate (1 mol) and L-tyrosine (1 mol) was prepared with 15 mL of distilled water in a 100 mL beaker. The mixture was stirred for 15 minutes at room temperature followed by addition of 10 mL of 0.15 M NaOH solution. Then the reaction mixture was kept for sonication under ultrasonication horn on 5 sec. pulse mode (5 sec. on mode and 5 sec. off mode) at 40% amplitude and measured. After completion of reaction, resultant product was washed with distilled water and absolute ethanol several times and dried in oven at 60 °C for 1 h.
- the white colored product was obtained and characterized with help of XRD, FEG-SEM, FT-IR, DSC-TGA techniques. Characterization of Synthesized Hybrid nanoflowers: The synthesized amino acid-zinc hydroxide hybrid complex nanomaterials were characterized using X-ray diffraction (XRD), fourier transform infrared spectroscopy (FTIR), UV-Vis spectrometer and confirmed hybrid material and also characterized with help of field emission gun- scanning electron microscopy (FEG-SEM), energy-dispersive X-ray spectroscopy (EDS), thermogravimetric analysis (TGA) techniques as disclosed in detail description of drawing.
- XRD X-ray diffraction
- FTIR Fourier transform infrared spectroscopy
- UV-Vis spectrometer UV-Vis spectrometer
- FEG-SEM field emission gun- scanning electron microscopy
- EDS energy-dispersive X-ray spectroscopy
- TGA thermogravimetric analysis
- Example 2 Method of Preparation: The mixture of zinc acetate (1 mol) and L-Valine(l mol) was prepared with 15 mL of distilled water in a 100 mL beaker. The mixture was stirred for 15 minutes at room temperature followed by addition of 10 mL of 0.15 M NaOH solution. Then the reaction mixture was kept for sonication under ultrasonication horn on 5 sec. pulse mode (5 sec. on mode and 5 sec. off mode) at 40% amplitude and measured. After completion of reaction, resultant product was washed with distilled water and absolute ethanol several times and dried in oven at 60 °C for 1 h.
- the white colored product was obtained and characterized with help of XRD, FEG-SEM, FT-IR, DSC-TGA techniques. Characterization of Synthesized Hybrid material: The synthesized amino acid-zinc hydroxide hybrid materials were characterized with help of field emission gun- scanning electron microscopy (FEG-SEM) as disclosed in drawing no 5.
- FEG-SEM field emission gun- scanning electron microscopy
- Example 3 Method of Preparation: The mixture of zinc acetate (1 mol) and L-Cystine (1 mol) was prepared with 15 mL of distilled water in a 100 mL beaker. The mixture was stirred for 15 minutes at room temperature followed by additionof 10 mL of 0.15 M NaOH solution. Then the reaction mixture was kept for sonication under ultrasonication horn on 5 sec. pulse mode (5 sec. on mode and 5 sec. off mode) at 40% amplitude and measured. After completion of reaction, resultant product was washed with distilled water and absolute ethanol several times and dried in oven at 60 °C for 1 h.
- the white colored product was obtained and characterized with help of XRD, FEG-SEM, FT-IR, DSC-TGA techniques. Characterization of Synthesized Hybrid material: The synthesized amino acid-zinc hydroxide hybrid materials were characterized with help of field emission gun- scanning electron microscopy (FEG-SEM) as disclosed in drawing no 6.
- FEG-SEM field emission gun- scanning electron microscopy
- Example 4 Method of Preparation: The mixture of zinc acetate (1 mol) and L-Proline(l mol) was prepared with 15 mL of distilled water in a 100 mL beaker. The mixture was stirred for 15 minutes at room temperature followed by addition of 10 mL of 0.15 M NaOH solution. Then the reaction mixture was kept for sonication under ultrasonication horn on 5 sec. pulse mode (5 sec. on mode and 5 sec. off mode) at 40% amplitude and measured. After completion of reaction, resultant product was washed with distilled water and absolute ethanol several times and dried in oven at 60 °C for 1 h.
- the white colored product was obtained and characterized with help of XRD, FEG-SEM, FT-IR, DSC-TGA techniques. Characterization of Synthesized Hybrid material: The synthesized amino acid-zinc hydroxide hybrid materials were characterized with help of field emission gun- scanning electron microscopy (FEG-SEM) as disclosed in drawing no 7.
- FEG-SEM field emission gun- scanning electron microscopy
- Example 5 Method of Preparation: The mixture of zinc acetate (1 mol) and L-tyrosine- Cystine (1 mol) was prepared with 15 mL of distilled water in a 100 mL beaker. The mixture was stirred for 15 minutes at room temperature followed by addition of 10 mL of 0.15 M NaOH solution. Then the reaction mixture was kept for sonication under ultrasonication horn on 5 sec. pulse mode (5 sec. on mode and 5 sec. off mode) at 40% amplitude and measured. After completion of reaction, resultant product was washed with distilled water and absolute ethanol several times and dried in oven at 60 °C for 1 h.
- the white colored product was obtained and characterized with help of XRD, FEG-SEM, FT- IR, DSC-TGA techniques. Characterization of Synthesized Hybrid material: The synthesized amino acid-zinc hydroxide hybrid materialwere characterized with help of field emission gun-scanning electron microscopy (FEG-SEM) as disclosed in drawing no 8.
- FEG-SEM field emission gun-scanning electron microscopy
- SEM scanning electron microscopy
- the figure 9 represent the zinc peptide nanoflowers like structures observe in NaOH matrix when we used L-Valine.precipitate was dried at high temperature (about 80°C) for 8 hours without washing.
- Figure 10 represent the Agglomerated crystals were observed in NaOH matrix when we usedD-Valine. precipitate was dried at high temperature (about 80°C) for 8 hours without washing.
- Figure 11 represent the nanoflowers were observed in NaOH matrix when we usedL5D5- Valine. precipitate was dried at temperature about 80°C for one daywithout washing.
- the FTIR spectra are as follows: a) FTIR of Zinc oxide - (L-Val ) peptide complex dried at about 80°C for one day b) FTIR of Zinc oxide - (D-Val ) peptide complex dried at about 80°C for one day c) FTIR of Zinc oxide - (L5D5-Val) peptide complex dried at about 80°C for one day. where L valine and D valine is in raito of 0.5:0.5.
- the figure 5 depict the XRD patterns for following samples:
- the figure 14 represents the zinc peptide nanoflowers and unorganized structures observe in NaOH matrix when we used D-Serine.
- the zinc oxide-peptide flowers were more aggregated due to the NaOH matrix. Next, washing was doneon theNaOH matrix with distilled water for several times and completely removed the NaOH.
- the present invention depict the determintic mechanism of supramolecularself assembly in precipitation is important step for homochiralty.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Polymers & Plastics (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Food Science & Technology (AREA)
- Zoology (AREA)
- Animal Husbandry (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Biophysics (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Peptides Or Proteins (AREA)
Abstract
The present invention relates to a novel amino acid/polypeptide-zinc oxide/ hydroxide hybridized nanomaterials and a preparation method thereof. The present invention further discloses the different type of hybrid nanomaterials comprising at least one amino acids and zinc oxide/hydroxide. The said nanomaterials are of definite crystal morphology. The process provided by the invention is simple, economic, and environmentally friendly and it has the advantage of providing controlled crystal morphology over uniform size. These hybrid materials may be further use in photodiodes and solar cells. The safety of metal- peptide complexes is enhanced by the use of natural amino acids and by improving its bioavailability to minimize the amount of metal added to the feed to meet the nutritional requirements of animals.
Description
TITLE
"NOVEL AMINO ACID/PEPTIDE-ZINC HYBRID NANOMATERIALS AND
PROCESS OF PREPARATION THEREOF"
CROSS-REFERENCE TO RELATED APPLICATIONS:
This application claims priority of Indian patent application no 1623/MUM/2015, filed 21/10/2015 and TEMP/E- 1/35206/2016-MUM dated 21/10/2016 the disclosure of which are incorporated herein by reference.
FIELD OF INVENTION
The present invention relates to a novel compound of zinc with amino acid or peptide in nanomaterials form. More preferably, the present invention further discloses the different type of hybrid nanomaterials comprising at least one amino acids and zinc oxide/hydroxide. The said nanomaterials are of definite crystal morphology. The process provided by the invention has the advantage of providing controlled crystal morphology over uniform size. The said complex have application in various industry more focused pharmaceutical area due to absorbability of the complex and the ability of the complex to participate in biochemical reactions. The safety of metal-amino acid/peptide complexes is enhanced by the use of natural amino acids and by improving its bioavailability to minimize the amount of metal added to the feed to meet the nutritional requirements of animals. These hybrid materials may be further use in photodiodes and solar cells.
BACKGROUND AND PRIOR ART OF THE INVENTION
Nano-technology has been widely used in various disciplines such as optical, electrical, magnetic and catalytic, and many other fieldswith a special appearance of complex new structure, it thus provide more opportunities to explore their new properties. Thus, researchers are working on nanomaterials composition, structure, shape, size and arrangement and other controls to be prepared in line with the intended function of various
nanomaterials. Organic-inorganic hybrid nanomaterial is the second single-component materials, composites and functionally graded materials after the 4th generation of new material, because of its constant matching the structure, scale, especially after reaching the nanoscale range to achieve a material properties within the scope of molecules, atoms and other controllable has become one of the most promising research directions in material science.
The inorganic-organic hybrid new material and its unique properties are widely used in the photodiodes and solar cells and other high-tech devices, thus leads to great deal of attention. The inorganic and organic materials together form a new type of special structure of an organic inorganic hybrid nanomaterial, it is possible to enhance the light, electric and magnetic properties of an inorganic material, and to improve the rigidity and thermal stability of the inorganic material, and also can improves morphological controllability as well as having excellent properties. Due to a combination of inorganic materials such respective advantages of organic materials, with high stability and rigidity, has many excellent properties in terms of mechanical, optical, thermal, electromagnetic and biology, and thus become a hot material science.
Amino acids are the basic constituents of life. They are biologically important organic compounds. Proteinogenic and non-proteinogenic amino acids are important in body functions, catalysis and as drugs. Decoration of nanop article surface by various proteins and amino acid has been proved as an effective strategy to improve biocompatibility of nanoparticles or functional nanoparticles. The reports on synthesis of amino acid-metal nanocomposite materials are available only for L-cystein-CuO hierarchical structure and L-Proline immobilized on ZnS nanoparticles. Also various organic material like protein, DNA, polysaccharides, collagen, chitosan, silica and polymers are combined with metals is the well known research area in organic-inorganic hybrid nanomaterials.
The conventional process for synthesis of nanocomposites utilizes complicated and tedious way of handling. Our invention reports the fabrication of organic -inorganic hybrid nanomaterials. The synthesis process is simple, green and economic for preparation of nanopartice of amino acid-zinc hydroxide hybrid complex.
WO2013003836 discloses a hybrid materials and nanocomposite materials comprising metal precursor compounds embedded in a carbon matrix. A method is reported for creating functional organic-inorganic hybrid materials by copolymerization of organic molecules and inorganic compounds.
Patent publication no. WO 2007124131 provides a contrast agent for magnetic resonance imaging (MRI) comprising a hybrid nanoparticle, said hybrid nanoparticle comprising: a polymeric matrix material; and a plurality of coordination complexes, each coordination complex comprising a functionalized chelating group and a paramagnetic metal ion, wherein the paramagnetic metal ion comprises an element selected from the group consisting of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, molybdenum, ruthenium, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, and ytterbium.
US patent No US 8,759,245, discloses a method for preparing iron -containing porous organic-inorganic hybrid materials where the organic compound ligand is bonded to a central metal.
European patent No EP2089313A2 provides Metal -polymer hybrid nanomaterials comprise nanotubes or nanowires and metal layers formed on the inner or outer surfaces of the nanotubes or the outer surfaces of the nanowires. The nanotubes or nanowires include a light- emitting π-conjugated polymer and the metal layers are composed of a metal whose surface plasmon energy level is close to the energy band gap of the nanotubes or nanowires.
CN104307573, discussed about protein inorganic hybrid nanomaterials, wherein:
a flower-shaped nano-materials made of metal phosphate and protein hybrid formation and said metal phosphate is Μη3(Ρ04)2, Zn3(P04)2 or Cu3(P04)2.
The present inventors have surprisingly invented the novel organic-inorganic hybrid nanomaterials i.e. amino acid/peptide doped with zinc hydroxide/oxide and method of synthesis thereof.
The novel amino acid-zinc oxide/ hydroxide hybrid nanoflowers comprising at least one amino acid and/or mixture thereof as organic moiety and inorganic moiety are of zincoxide/ hydroxide.
Also the presence of essential metals (trace elements) in sufficient quantities and in a biologically available form in diet is essential for maintaining the health and well-being of domestic animals and poultry.The identification of metal-associated biomolecules has led to the use of the bioinspired/biomimetic approach for synthesis of such type of essential materials. E.g. The coordination of Zn2+ with proteins plays an important role for the structural stability and functionality of proteins in living organisms as evidenced in metalloproteins such as metallothionine and zinc fingers of DNA -binding proteins.
US8,741,375 B2, discloses a mixed amino acid metal salt complex of the amino acids, lysine and glutamic acid associated with trace metals selected from the group consisting of iron, manganese, copper and zinc to provide highly bioavailable sources of the iron, manganese, copper and zinc and different amino acid transport pathways of lysine and glutamic acid.
US5, 698,724 A discloses the method and composition involves preparing a high yield of a metal amino acid complex, visible as a source of highly bioavailable transition metal ions, highly bioavailable essential amino acid for a livestock animal is disclosed.
CN 101905328 provide a method for preparing watersolubleAulOnanocluster molecules. The invention discloses a method for preparing watersolubleAulO nanocluster molecules through a biomolecule induction onestepreaction. The methodcomprises the following steps of: 1) dissolving histidine in water and stirring the solution to obtain 0.0033 to 0.2 M aqueous solution of the histidine; 2) dissolvingchloroauric acid in the water and stirring the solution to obtain 10 mM aqueous solution of the chloroauric acid; and 3) adding 3 mL of the 0.0033 to 0.2 Maqueous solution of the histidine into 1 mL of the 10 mM aqueous solution of thechloroauric acid, adjusting the pH value of the solution to be between 2 and
11, fully mixing and standing for 1 hour to obtain the watersolubleAulO nanocluster molecules. A watersolublenanoclustersAulO obtained by the method emits a bluegreenfluorescent light and the fluorescence quantum efficiency is 8.78 percent;
The synthesis of peptide from pure amino acids, one -pot dehydration-hydration condensation of amino acids forming oligopeptide chains with fifty percent yield is reported. Moreover, Use of exotic coupling reagent in stochiometric amount during current proactive of amide bond formation make the process poor atom economical. Circular polarized lighst, enantioselective photochemistry, magnetochiraldichroism, magnetic field is among most interesting topics which were explored to understand homochiralitybut it produces only small enantiomeric excess.
Theoretical studies for origin of biological homochirality proposes two mechanistic theories. One is based on random chance or static fluctuation which implicatehomochirality and second proposed that homochirality is result of deterministic effect of physical force.Unresolved Quest of first step of biochemical processes that can convert mirror symmetric molecular chirality of amino acid to complete asymmetric state is particularly interest to chemistry, biology and physics.
It would therefore be desirable to provide a process by which metal complex containing a peptide bond may be synthesize which exhibit completechiroselective properties. It is a primary objective of the present invention to fulfill this need.
The inventors have also developed a simple method to synthesis said hybrid nanomaterials by ultrasonication which is offering many advantages like simple, green, economically effective, non-toxic with less reaction time. As the need of environmental protection chemicals used in this preparation is non-toxic and inexpensive.
Hence, the present inventors has surprisingly found the process for novel zinc peptide nanomaterialsusing pure amino acid as the starting reactant to prepare themetal peptide complex which exhibit complete enantioselectiveself assembly.
The present invention offers a solution by enantioselectivesupramolecularself organization of unactivated amino acids with Zinc. Here current invention shows enantioselectiveself organization of zinc peptide nanomaterials from single or multiple amino acids in water at desired temperature without using any coupling reagent or activated amino acid.
The said complex have application in pharmaceutical area due to absorbability of the complex and the ability of the complex to participate in biochemical reactions. The safety of metal-peptide complexes is enhanced by the use of natural amino acids and by improving its bioavailability to minimize the amount of metal added to the feed to meet the nutritional requirements ofanimals.
The discussion of documents, acts, materials, devices, articles and the like is included in this specification solely for the purpose of providing a context for the present invention. It is not suggested or represented that any or all of these matters formed part of the prior art base or were common general knowledge in the field relevant to the present invention as it existed before the priority date of each claim of this application.
OBJECTIVES OF THE INVENTION
The main objective of present invention is to provide novel nanomaterials of amino acid- zinc oxide/ hydroxide hybrid complex.
The primary objective of the present invention is to provide a novel zinc oxide peptide complexnanomaterials.
The main objective of present invention is to provide novel method for preparation of nanomaterials of amino acid-zinc hydroxide hybrid complex.
A further objective of the present invention is to provide aprocess for preparation of zinc oxide peptide complex.
The further object of the invention is to provide amino acid-zinc hydroxide hybrid nanomaterials with size ranges from 30 nm to 6 μηι.
Another object of the invention is to develop a novel method for preparation of amino acid-zinc hydroxide nanomaterials using low cost and easily available, less toxic, inexpensive chemicals.
• A further objective of the invention is to provide a process for synthesis of enenatioselective zinc oxide peptide complexnanomaterials.
• Another objective of the invention is to provide a simple self assembling process of peptide from precursor of amino acids at desired temperature.
SUMMARY OF INVENTION
The novel Hybrid nano-material complexes described in this invention are represented by general formula (I);
ZO-(R)y
FORMULA (I)
wherein "ZO" is selected from Zinc oxide, Zinc Hydroxide
"R" is polypeptide, amino acid
"y" is integer from 2 to 10
Andwherein the diameter of said hybrid nano - material is from 30 nm to 6000 nm having controlled crystal morphology.
The present invention relates to a novel amino acid-zinc oxide/ hydroxide hybrid nano materials and a preparation method thereof. More preferably, the present invention is providing a novel organic-inorganic nano-sized hybrid material wherein one amino acid or more than one amino acid is coupled with zinc hydroxide. Morphology of final amino acid-zinc hydroxide hybrid nanomaterials is depending upon the type of amino acid present in complex. The present invention also relates to process for synthesis of said novel hybrid nanomaterials, which controls the overall crystal morphology of hybrid nanomaterials. In case of L-tyrosine the formation of hybrid nanoflowers has controlled uniform size ranging from 500 nm to 600 nm, with uniformly growing slices of petals or needles ranging from 40 nm to 60 nm.
In accordance to one of the important embodiment, the said peptide bond isself assembled from the number of amino acids at the time of synthesis of complex.
BRIEF DESCRIPTION OF DRAWINGS:
For a more complete understanding of the features and advantages of the present invention, reference is now made to the detailed description of the invention along with the accompanying figures and in which:
FIGURE1: Depict the XRD comparisons of (a) pure amino acid (i.e., L-Tyrosine) (b) pure Zn(OH)2 (c) L-Tyrosine- Zn(OH)2 hybrid nanoflowers (d) L-Tyrosine (blue) and Zn(OH)2 (red).
FIGURE2: Depict the FEG-SEM images of L-Tyrosine-zinc hydroxide hybrid nanoflowers obtained in example 1.
FIGURE3: Depict the FT-IR Spectra of L-Tyrosine-zinc hydroxide hybrid nanoflowers obtained in example 1.
FIGURE4: Depict the EDS spectrum of amino acid-zinc hydroxide hybrid nanoflowers obtained in example 1.
FIGURE5: Depict the FEG-SEM images of Zinc Hydroxide -Valine hydride nano- material obtained in example 2.
FIGURE6: Depict the FEG-SEM images of Zinc Hydroxide-Cystiene hydride nano- material obtained in example 3.
FIGURE7: Depict the FEG-SEM images of Zinc Hydroxide-Proline hydride nano- material obtained in example 4.
FIGURE8: Depict the FEG-SEM images of Zinc oxide-Tyrosine/Cystiene hydride nano- material obtained in example 5.
FIGURE 9:Depict the SEM images of zinc oxide peptide wherein nanoflowers like structures observe in NaOH matrix when amino acid is L- Valine.
FIGURE 10:Depict the SEM images of zincoxide peptide wherein nanoflower were observed in NaOH matrix when amino acid isD-Valine.
FIGURE ll:Depict the SEM images ofzincoxide peptide wherein dense nanoflower crystals were observed in NaOH matrix when amino acid is L- Valine and D-Valine is in 0.5:0.5 ratio.
FIGURE 12:Depict FT-IR spectras Pattern of different complex.
FIGURE13:Depict X-ray Diffraction Pattern of different complex.
FIGURE 14:Depict the SEM images of zinc oxide peptide wherein agglomerated nanoflower were observed in NaOH matrix when amino acid isL-Serine.
FIGURE 15:Depict the SEM images of zinc peptide wherein agglomeratednanoflower and unorganized crystals were observed in NaOH matrix when amino acid isD-Serine .
FIGURE16 :Depict the SEM images of zinc oxide peptide wherein
agglomeratednanoflowercrystals were observed in NaOH matrix when amino acid isL- Serine and D-Serine is in raotio of 0.5:0.5.
DETAILED DESCRIPTION OF THE INVENTION
The making and using of various embodiments of the present invention are discussed in detail below as it should be appreciated that the present invention provides many applicable inventive concepts that can be embodied in a wide variety of specific contexts. The specific embodiments discussed herein are merely illustrative of specific ways to make and use the invention and do not delimit the scope of the invention.
To facilitate the understanding of this invention, a number of terms are defined below. Terms defined herein have meanings as commonly understood by a person of ordinary skill in the areas relevant to the present invention. Terms such as "a", "an" and "the" are not intended to refer to only a singular entity, but include the general class of which a specific example may be used for illustration. The terminology herein is used to describe specific embodiments of the invention, but their usage does not delimit the invention, except as outlined in the claims.
The novel Hybrid nano-material complexes described in this invention are represented by general formula (I);
ZO-(R)y
FORMULA (I)
wherein "ZO" is selected from Zinc oxide, Zinc Hydroxide
"R" is polypeptide, amino acid
"y" is integer from 2 to 10
andwherein the diameter of said hybrid nano - material is from 30 nm to 6000 nm having controlled crystal morphology.
The present invention involves the design, synthesis and evaluation of novel safe and effective zinc oxide/hydroxidepeptide/amino acid nanomaterials. More preferably, the present invention provides anenantioselective compounds of zinc oxide peptide nanomaterials and zinc hydroxide aminoacid nanomaterial. Features that impart biological activity to metal-peptide complexesincludehomochirality, cooperativetyeffect.Stability of the complex at the pHs of the GI contents, absorbability of the complex and the ability of the complex to participate in biochemical reactions. The safety of metal-peptide complexes is enhanced by the use of natural amino acids and by improving its bioavailability to minimize the amount of metal added to the feed to meet the nutritional requirements ofanimals.
Accordingly one of the embodiments, the present invention is providing novel amino acid- zinc hydroxide hybrid complex nanomaterial. The said hybrid nanomaterials comprises of at least one amino acid forming a hybrid complex with inorganic zinc hydroxide in the molar ratio of 0.3: 1 to 2: 1; wherein the crystal diameter of said hybrid nano-material is in the of 30 nm to 6 μπι and having control crystal morphology.
Also, accordingly second embodiment, the present invention provides a method for preparing amino acid-zinc hydroxide hybrid nanomaterial having a relatively small nano particle size and control crystal morphology through an environmentally friendly method. The observed crystal morphology is flower shape, bi-pyramidal shape, wulfenite shape, needle shape and rod shape of nanomaterial and microcrystals.
In the preferred embodiment of present invention, the said amino acids are selected from a group of non-polar aliphatic side group's, aromatic side groups, polar uncharged side groups and positively charged side groups amino acid.
More preferably, the selected amino acids are Valine, aromatic side group's amino acid (Tyrosine), polar uncharged side groups amino acid (Proline) and positively charged side groups amino acid (histidene).
The present invention is not limited to the amino acids disclosed herein. Rather, any suitable amino acid can be used to prepare the hybrid material in accordance with the various methods disclosed herein.
More preferably the amino acid are selected from proteinogenic amino acids and non- proteinogenic amino acids, a tyrosine, cysteine, valine, proline, histidene or mixture thereof.
Accordingly second embodiment of present invention, it provides a method of preparation of amino acid- zinc hydroxide hybrid complex comprising steps of: a. Preparation of reaction mixture containing zinc precursor and at least one amino acid in presence of reagent, zinc precursor is selected from zinc acetate.The said reagent is selected from sodium hydroxide, Potassium hydroxide and amino acid is selected from a group of non-polar aliphatic side groups amino acid, aromatic side groups amino acid, polar uncharged side groups amino acid and positively charged side groups amino acid. b. Treating the said reaction mixture with ultrasonic frequencies using probe sonicator. The ultrasonic frequencies are in the range from 20 kHz to 40 kHz. c. Washing of product obtained in step b) with solvent like ethanol and water or their mixture d. Drying of sample is done at temperature between 20 °C to 70 °C for a time period of 10 min to 2 hr.
The nanomaterial having a crystal diameter of 30 nm to 6 μπι is formed at ultrasonic range of 20 kHz to 40 kHz and 40% amplitude performed for 5 sec. on/off mode,
wherein the solvent used to prepare the precursor solution and amino acid solution is selected from water only.
Drying temperature of the synthesized materials mainly depending on amino acid used with Zn precursor, Ex.- For histidine, room temperature is good for drying.
The synthesis of various amino acids-zinc hydroxide hybrid complexes using combination of one or more amino acids can be done using this method. The presence of each amino acid in the nanomaterials was also confirmed by ninhydrin test for amino acid with change in color. The process can be applicable to all type of amino acids z.e.proteinogenic amino acids and non- proteinogenic amino acids preferably amino acids such as Tyrosine, Cystiene, Valine, Proline, Histidene.
Accordingly another embodiment of invention, the process is suitably controls the morphology of nanomaterials. In case of L-Tyrosine, the shape of resulting amino acid- zinc hydroxide hybrid complex nanomaterials is nanoflowers, however shape and size of amino acid-zinc hydroxide hybrid complex nanomaterials changes with changes in amino acids. Morphology of amino acid-zinc hydroxide hybrid nanoflowers with L-Tyrosine is controlled over uniform size ranging from 500 nm to 600 nm, with uniformly growing slices of petals ranging from 40 nm to 60 nm. The synthesized amino acid-zinc hydroxide hybrid complex nanomaterial comprises of formation of peptide bond linkage with one or two amino acids. The solvent used is any volatile alcohols like methanol, ethanol, propanol, isopropyl alcohol with or without mixture of water.
In accordance to one of the important embodiment, the said peptide bond isself assembled from the number of amino acids at the time of synthesis of complex.
In accordance to second embodiment, the parent amino acids are selected from but not limited toarginine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, threonine, tryptophan valine, glycine, etc and mixture thereof.
Theseamino acid exist in enantio pure form.
In accordance to further embodiment, The present invention alsoprovides a process for enantioselective control over structure and physicochemical properties of zinc peptide nanomaterials.Andvisual discrimination in hybrid nanostructures with enantioselective L- and D-amino acid through the self assembly during peptide bond formation.
Considering morphology for each and every amino acid and its combination is different. Depending on parameters and other factors morphology differs, like for
Isoleucine, leucine, lysine, methionine, phenylalanine, threonine, tryptophan valine, glycine, arginine, nanoflower,nano wire, nano tube, various other as required are obtained depending on combination of amino acid, histidineforms gel which has various application and which later on is converted in to nanowires.
The chiroselective zinc peptide nanostructures is precipitated out by the addition of zinc acetate, amino acid with sodium hydroxidein alkalinewater. Further drain out a aqueous layer and drying out precipitate at room temperature (31°C) for more than 48 hr.
Zinc oxide peptide nanostructure is prepared by adding zinc precussor with amino acid and solvent. This solution is stirred till complete dissolution is done. Alkali is added with stirring and precipitate is obtain. Heating is done later washing and filteration is doneand final product is obtained.
Zinc precussor is not limiting to zinc acetate, zinc sulphate etc.
In according to present invention the zinc precursor is preferably selected form zinc acetate.
In one of the embodiment the solvent used in the process is water, alcohol or combination thereof.
Alkali used could be sodium hydroxide, potassium hydroxide.
The present invention is further described with the help of the following examples, which are given by way of illustration and therefore should not be construed to limit the scope of the invention in any manner.
Examples:
Example 1: Method of Preparation: The mixture of zinc acetate (1 mol) and L-tyrosine (1 mol) was prepared with 15 mL of distilled water in a 100 mL beaker. The mixture was stirred for 15 minutes at room temperature followed by addition of 10 mL of 0.15 M NaOH solution. Then the reaction mixture was kept for sonication under ultrasonication horn on 5 sec. pulse mode (5 sec. on mode and 5 sec. off mode) at 40% amplitude and measured. After completion of reaction, resultant product was washed with distilled water and absolute ethanol several times and dried in oven at 60 °C for 1 h. The white colored product was obtained and characterized with help of XRD, FEG-SEM, FT-IR, DSC-TGA techniques. Characterization of Synthesized Hybrid nanoflowers: The synthesized amino acid-zinc hydroxide hybrid complex nanomaterials were characterized using X-ray diffraction (XRD), fourier transform infrared spectroscopy (FTIR), UV-Vis spectrometer and confirmed hybrid material and also characterized with help of field emission gun- scanning electron microscopy (FEG-SEM), energy-dispersive X-ray spectroscopy (EDS), thermogravimetric analysis (TGA) techniques as disclosed in detail description of drawing.
Example 2: Method of Preparation: The mixture of zinc acetate (1 mol) and L-Valine(l mol) was prepared with 15 mL of distilled water in a 100 mL beaker. The mixture was stirred for 15 minutes at room temperature followed by addition of 10 mL of 0.15 M NaOH solution. Then the reaction mixture was kept for sonication under ultrasonication horn on 5 sec. pulse mode (5 sec. on mode and 5 sec. off mode) at 40% amplitude and measured. After completion of reaction, resultant product was washed with distilled water and absolute ethanol several times and dried in oven at 60 °C for 1 h. The white colored product was obtained and characterized with help of XRD, FEG-SEM, FT-IR, DSC-TGA techniques. Characterization of Synthesized Hybrid material: The synthesized amino
acid-zinc hydroxide hybrid materials were characterized with help of field emission gun- scanning electron microscopy (FEG-SEM) as disclosed in drawing no 5.
Example 3: Method of Preparation: The mixture of zinc acetate (1 mol) and L-Cystine (1 mol) was prepared with 15 mL of distilled water in a 100 mL beaker. The mixture was stirred for 15 minutes at room temperature followed by additionof 10 mL of 0.15 M NaOH solution. Then the reaction mixture was kept for sonication under ultrasonication horn on 5 sec. pulse mode (5 sec. on mode and 5 sec. off mode) at 40% amplitude and measured. After completion of reaction, resultant product was washed with distilled water and absolute ethanol several times and dried in oven at 60 °C for 1 h. The white colored product was obtained and characterized with help of XRD, FEG-SEM, FT-IR, DSC-TGA techniques. Characterization of Synthesized Hybrid material: The synthesized amino acid-zinc hydroxide hybrid materials were characterized with help of field emission gun- scanning electron microscopy (FEG-SEM) as disclosed in drawing no 6.
Example 4: Method of Preparation: The mixture of zinc acetate (1 mol) and L-Proline(l mol) was prepared with 15 mL of distilled water in a 100 mL beaker. The mixture was stirred for 15 minutes at room temperature followed by addition of 10 mL of 0.15 M NaOH solution. Then the reaction mixture was kept for sonication under ultrasonication horn on 5 sec. pulse mode (5 sec. on mode and 5 sec. off mode) at 40% amplitude and measured. After completion of reaction, resultant product was washed with distilled water and absolute ethanol several times and dried in oven at 60 °C for 1 h. The white colored product was obtained and characterized with help of XRD, FEG-SEM, FT-IR, DSC-TGA techniques. Characterization of Synthesized Hybrid material: The synthesized amino acid-zinc hydroxide hybrid materials were characterized with help of field emission gun- scanning electron microscopy (FEG-SEM) as disclosed in drawing no 7.
Example 5: Method of Preparation: The mixture of zinc acetate (1 mol) and L-tyrosine- Cystine (1 mol) was prepared with 15 mL of distilled water in a 100 mL beaker. The mixture was stirred for 15 minutes at room temperature followed by addition of 10 mL of 0.15 M NaOH solution. Then the reaction mixture was kept for sonication under ultrasonication horn on 5 sec. pulse mode (5 sec. on mode and 5 sec. off mode) at 40%
amplitude and measured. After completion of reaction, resultant product was washed with distilled water and absolute ethanol several times and dried in oven at 60 °C for 1 h. The white colored product was obtained and characterized with help of XRD, FEG-SEM, FT- IR, DSC-TGA techniques. Characterization of Synthesized Hybrid material: The synthesized amino acid-zinc hydroxide hybrid materialwere characterized with help of field emission gun-scanning electron microscopy (FEG-SEM) as disclosed in drawing no 8.
Example 6: Synthesis of Zinc oxide-polypeptide of L or D-Valine amino acid:
The chiroselective zinc peptide nanostructures were discovered in precipitate formed by the addition of zinc acetate, valine with sodium hydroxide (pH = 11) in water. The supernatant was drain out and precipitate was dried at high temperature (about 80°C) for 8 hours without washing.
A. Scanning electron microscopy Analysis: The scanning electron microscopy (SEM) images display the formation of hierarchical structures of peptide nanomaterials at room temperature.
The figure 9 represent the zinc peptide nanoflowers like structures observe in NaOH matrix when we used L-Valine.precipitate was dried at high temperature (about 80°C) for 8 hours without washing.
Figure 10 represent the Agglomerated crystals were observed in NaOH matrix when we usedD-Valine. precipitate was dried at high temperature (about 80°C) for 8 hours without washing.
Figure 11 represent the nanoflowers were observed in NaOH matrix when we usedL5D5- Valine. precipitate was dried at temperature about 80°C for one daywithout washing.
Further the, dried precipitate was washed with distilled water for several times until NaOH removed completely and the formation of uniform size and uniform shape of enantioselective zinc peptide hybrid nanomaterials was observed.
B. Fourier transforminfraredAnalysis: Fourier transform infrared (FT-IR) spectra of nanomaterials help to understand the formation of L -Serine peptide and D -Serine peptide with zinc oxide at room temperature and Zinc oxide at 80C.
As depicted in figure 12, the FTIR spectra are as follows: a) FTIR of Zinc oxide - (L-Val ) peptide complex dried at about 80°C for one day b) FTIR of Zinc oxide - (D-Val ) peptide complex dried at about 80°C for one day c) FTIR of Zinc oxide - (L5D5-Val) peptide complex dried at about 80°C for one day. where L valine and D valine is in raito of 0.5:0.5.
C. X-ray diffraction Analysis:The X-ray diffraction pattern of the nanoflowers fits with that of plain ZnO and.
The figure 5 depict the XRD patterns for following samples:
a. XRD pattern of Zinc oxide - (L-Serine) peptide complex dried at room temperature for one day
b. XRD pattern of Zinc oxide - (D-Serine) peptide complex dried at room temperature for one day
c. XRD pattern of Zincoxide - (L5D5-Serine) where L serine and D serine is in raito of 0.5:0.5 ,peptide complex dried at room temperature for one day.
Example 7: Synthesis of Zinc oxide-polypeptide of L or D-Serine amino acid:
The chiroselective zinc peptide nanostructures were discovered in precipitate formed by the addition of zinc acetate, Serine with sodium hydroxide (pH = 11) in water. The supernatant was drain out and precipitate was dried at room temperature for one daywithout washing.
A. SEM analysis: The formation of flower like structure of zinc oxide— peptide nanostructures in NaOH matrix was observed when the reaction was carried out between
zinc acetate and L-Serine in presence of NaOH, and dried room temprature for one dayand SEM image is represented in figure 13.
The figure 14 represents the zinc peptide nanoflowers and unorganized structures observe in NaOH matrix when we used D-Serine.
The zinc oxide-peptide flowers were more aggregated due to the NaOH matrix. Next, washing was doneon theNaOH matrix with distilled water for several times and completely removed the NaOH.
When L-serine and D-serine is in 0.5:0.5 raitio, SEM images displays the dense nanoflowerwith definite shape and size as shown in figure 15.
The present invention depict the determintic mechanism of supramolecularself assembly in precipitation is important step for homochiralty.
The above embodiments are to be understood as illustrative examples of the invention. Further embodiments of the invention are envisaged. It is to be understood that any feature described in relation to any one embodiment may be used alone, or in combination with other features described, and may also be used in combination with one or more features of any other of the embodiments, or any combination of any other of the embodiments. Furthermore, equivalents and modifications not described above may also be used without departing from the scope of the invention, which is defined in the accompanying claims.
Claims
1. Hybrid nano-material having general formula (I);
ZO-(R)y
FORMULA (I)
wherein "ZO" is selected from Zinc oxide, Zinc Hydroxide
"R" is polypeptide, amino acid
"y" is integer from 1 to 10
andwherein the diameter of said hybrid nano - material is from 30 nm to 6000 nm having controlled crystal morphology.
2. Hybrid nano - material as claimed in claim 1 wherein polypeptide -Zinc oxide hybrid nano-material comprises at least one amino acid and zinc oxide in the molar ratio of 1: 1 to 10: 1.
3. Hybrid nano-material as claimed in claim 1 wherein amino acid -Zinc Hydroxide hybrid nano-material comprises at least one amino acid and Zinc Hydroxide in the molar ratio of 0.3 : 1 to 2: 1.
4. Hybrid nano-material as claimed in claim 1 wherein amino acid is selected from a group of non polar aliphatic side groups amino acid (Valine), aromatic side groups amino acid (Tyrosine), polar uncharged side groups amino acid (Proline) and positively charged side groups amino acid (histidene).
5. Hybrid nano-material as claimed in claim 4 wherein amino acid is selected from arginine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, threonine, tryptophan valine, glycine and mixture thereof.
6. Hybrid nano-material as claimed in claim 1 wherein the control crystal morphology is flower, bi-pyramidal, wulfnite, needle, rod, wire, tube and in gelform.
7. Hybrid nano-material as claimed in claim 2 wherein polypeptide -Zinc oxide hybrid nano-material comprises at least one amino acid and zinc oxide in the molar ratio preferably of 1: 1 to 3: 1.
8. A method for the synthesis of Hybrid nano-material having general formula (I) of claim 1 comprising steps of:
a) Preparation of reaction mixture containing zinc precursor and at least one amino acid in presence of solvent,
b) Addition of alkali and stirring till precipitation is obtained,
c) Optionally heating or sonication the above solution,
d) Separation.
9. The method for the synthesis of Hybrid nano-material as claimed in claim 8, wherein the said solvent is selected from water, alcohol or combination thereof.
10. The method for the synthesis of Hybrid nano-material as claimed in claim 8, wherein the alkali reagent is selected from sodium hydroxide, potassium hydroxide.
A method for the synthesis of Hybrid nano-material as claimed in claim 8, wherein the ultra sound sonication is carried out at the ultrasonic frequencies in the range from 20 kHz to 40 kHz and and 40% amplitude performed for 5 sec. on/off mode.
11. The method for the synthesis of Hybrid nano-material as claimed in claim 8 wherein zinc precursor is zinc acetate.
12. The method for the synthesis of Hybrid nano-material as claimed in claim 8, wherein the said separation includes drying, decanding, filtration, heating, washing and combination thereof.
13. The method for the synthesis of Hybrid nano-material as claimed in claim 8, wherein amino acid is selected from a group of non polar aliphatic side groups amino acid (Valine), aromatic side groups amino acid (Tyrosine), polar uncharged side groups amino acid (Proline) and positively charged side groups amino acid (histidene).
14. The method for the synthesis of Hybrid nano-material as claimed in claim 13, wherein amino acid is selected from arginine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, threonine, tryptophan valine, glycine and mixture thereof.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IN1623/MUM/2015 | 2015-10-21 | ||
IN1623MU2015 | 2015-10-21 | ||
INTEMP/E-1/35206/2016-MUM | 2016-10-21 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2017068548A1 true WO2017068548A1 (en) | 2017-04-27 |
Family
ID=58557038
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/IB2016/056356 WO2017068548A1 (en) | 2015-10-21 | 2016-10-21 | Novel amino acid/peptide-zinc hybrid nanomaterials and process of preparation thereof |
Country Status (1)
Country | Link |
---|---|
WO (1) | WO2017068548A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114096330A (en) * | 2020-06-02 | 2022-02-25 | 维白奥锤有限公司 | Metal phase change compound and preparation method thereof |
US11278512B2 (en) * | 2019-08-21 | 2022-03-22 | Brain Chemistry Labs | Compositions comprising a metal and L-serine, and uses thereof |
CN114988455A (en) * | 2022-05-17 | 2022-09-02 | 刘天龙 | Method for preparing nano zinc oxide in large quantity |
CN115043744A (en) * | 2022-06-22 | 2022-09-13 | 西北工业大学 | Preparation method of self-assembled amino acid nano material |
-
2016
- 2016-10-21 WO PCT/IB2016/056356 patent/WO2017068548A1/en active Application Filing
Non-Patent Citations (1)
Title |
---|
MEGHANA RAMANI ET AL.: "Amino acid-mediated synthesis of zinc oxide nanostructures and evaluation of their facet-dependent antimicrobial activity'';", COLLOIDS AND SURFACES B: BIOINTERFACES;, vol. 117, 4 March 2014 (2014-03-04), pages 233 - 239, XP028647170 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11278512B2 (en) * | 2019-08-21 | 2022-03-22 | Brain Chemistry Labs | Compositions comprising a metal and L-serine, and uses thereof |
CN114096330A (en) * | 2020-06-02 | 2022-02-25 | 维白奥锤有限公司 | Metal phase change compound and preparation method thereof |
EP3950717A4 (en) * | 2020-06-02 | 2022-11-02 | Webiotree Co., Ltd. | Metal compound having phase transformation, and preparation method thereof |
CN114096330B (en) * | 2020-06-02 | 2023-04-04 | 维白奥锤有限公司 | Metal phase change compound and preparation method thereof |
CN114988455A (en) * | 2022-05-17 | 2022-09-02 | 刘天龙 | Method for preparing nano zinc oxide in large quantity |
CN115043744A (en) * | 2022-06-22 | 2022-09-13 | 西北工业大学 | Preparation method of self-assembled amino acid nano material |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2017068548A1 (en) | Novel amino acid/peptide-zinc hybrid nanomaterials and process of preparation thereof | |
Zhang et al. | Synthesis of lanthanum doped carbon dots for detection of mercury ion, multi-color imaging of cells and tissue, and bacteriostasis | |
Wang et al. | Green preparation of carbon dots for intracellular pH sensing and multicolor live cell imaging | |
Wang et al. | Protein-directed synthesis of pH-responsive red fluorescent copper nanoclusters and their applications in cellular imaging and catalysis | |
Qin et al. | Highly water-dispersible TiO 2 nanoparticles for doxorubicin delivery: effect of loading mode on therapeutic efficacy | |
Moradi et al. | Green synthesis and characterization of magnetic NiFe 2 O 4@ ZnO nanocomposite and its application for photocatalytic degradation of organic dyes | |
Khandare et al. | PEG-conjugated highly dispersive multifunctional magnetic multi-walled carbon nanotubes for cellular imaging | |
EP2184262B1 (en) | Process for production of surface-coated inorganic particles | |
JP5008607B2 (en) | Method for producing high-yield bioimaging nanoparticles by early introduction of irregular surface structures | |
Sharma et al. | 92 years of zinc oxide: has been studied by the scientific community since the 1930s-An overview | |
CN105969331A (en) | Preparation method of nano-material suitable for targeting drug carriers | |
Al-Azawi et al. | Synthesis of silica nanoparticles via green approach by using hot aqueous extract of Thuja orientalis leaf and their effect on biofilm formation. | |
Kolanowska et al. | Carbon quantum dots from amino acids revisited: Survey of renewable precursors toward high quantum-yield blue and green fluorescence | |
KR20100004220A (en) | Ph sensitive metal nonaparticles and manufacturing mehtods thereof | |
Xie et al. | Amino-acid-mediated biomimetic formation of light-harvesting antenna capable of hydrogen evolution | |
Katkova | Water-soluble polynuclear metallamacrocyclic copper (II) and lanthanide (III) complexes based on amino hydroxamic acids | |
Jia et al. | Visible light-induced lanthanide polymer nanocomposites based on clays for bioimaging applications | |
Shah et al. | Synthesis and characterization of magnetite nanoparticles having different cover layer and investigation of cover layer effect on the adsorption of lysozyme and bovine serum albumin | |
KR20160089220A (en) | Fluorescent and magnetic core-shell nanochain structures and preparation method thereof | |
Zadehnazari | Metal oxide/polymer nanocomposites: A review on recent advances in fabrication and applications | |
Zhang et al. | Facile controlled preparation of phosphonic acid-functionalized gold nanoparticles | |
Varol et al. | Crystallization at nanodroplet interfaces in emulsion systems: A soft-template strategy for preparing porous and hollow nanoparticles | |
Xu et al. | Nontraditional luminescent molecular aggregates encapsulated by wormlike silica nanoparticles for latent fingerprint detection | |
Żebrowska et al. | Facile and controllable growth of β-FeOOH nanostructures on polydopamine spheres | |
EP2736052A1 (en) | A metal and metal oxide material having an organic surface modification and manufacturing method therefor |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 16857027 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 16857027 Country of ref document: EP Kind code of ref document: A1 |