CN115007113B - 一种掺杂碳点的壳聚糖膜及其制备与应用 - Google Patents
一种掺杂碳点的壳聚糖膜及其制备与应用 Download PDFInfo
- Publication number
- CN115007113B CN115007113B CN202110234611.2A CN202110234611A CN115007113B CN 115007113 B CN115007113 B CN 115007113B CN 202110234611 A CN202110234611 A CN 202110234611A CN 115007113 B CN115007113 B CN 115007113B
- Authority
- CN
- China
- Prior art keywords
- carbon
- chitosan
- doped
- glutaraldehyde
- chitosan film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 26
- 229910052799 carbon Inorganic materials 0.000 title claims description 26
- 239000000463 material Substances 0.000 claims abstract description 44
- 102000002068 Glycopeptides Human genes 0.000 claims abstract description 41
- 108010015899 Glycopeptides Proteins 0.000 claims abstract description 41
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000003463 adsorbent Substances 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002013 hydrophilic interaction chromatography Methods 0.000 claims abstract description 11
- 239000012472 biological sample Substances 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 238000006482 condensation reaction Methods 0.000 claims abstract description 5
- 241001465754 Metazoa Species 0.000 claims abstract description 3
- 210000001124 body fluid Anatomy 0.000 claims abstract description 3
- 239000010839 body fluid Substances 0.000 claims abstract description 3
- VUHRDFPZVYBHCU-UHFFFAOYSA-N [C].O=CCCCC=O Chemical compound [C].O=CCCCC=O VUHRDFPZVYBHCU-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 3
- 238000007710 freezing Methods 0.000 claims description 3
- 230000008014 freezing Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- -1 ammonia aldehyde Chemical class 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 239000012528 membrane Substances 0.000 abstract description 17
- DQJCDTNMLBYVAY-ZXXIYAEKSA-N (2S,5R,10R,13R)-16-{[(2R,3S,4R,5R)-3-{[(2S,3R,4R,5S,6R)-3-acetamido-4,5-dihydroxy-6-(hydroxymethyl)oxan-2-yl]oxy}-5-(ethylamino)-6-hydroxy-2-(hydroxymethyl)oxan-4-yl]oxy}-5-(4-aminobutyl)-10-carbamoyl-2,13-dimethyl-4,7,12,15-tetraoxo-3,6,11,14-tetraazaheptadecan-1-oic acid Chemical compound NCCCC[C@H](C(=O)N[C@@H](C)C(O)=O)NC(=O)CC[C@H](C(N)=O)NC(=O)[C@@H](C)NC(=O)C(C)O[C@@H]1[C@@H](NCC)C(O)O[C@H](CO)[C@H]1O[C@H]1[C@H](NC(C)=O)[C@@H](O)[C@H](O)[C@@H](CO)O1 DQJCDTNMLBYVAY-ZXXIYAEKSA-N 0.000 abstract description 12
- 230000004048 modification Effects 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- 238000005580 one pot reaction Methods 0.000 abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 2
- 230000002255 enzymatic effect Effects 0.000 description 13
- 239000000413 hydrolysate Substances 0.000 description 12
- 238000001819 mass spectrum Methods 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 229940027941 immunoglobulin g Drugs 0.000 description 7
- 239000011148 porous material Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 229940098197 human immunoglobulin g Drugs 0.000 description 5
- DTQVDTLACAAQTR-UHFFFAOYSA-N trifluoroacetic acid Substances OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 5
- 102000035122 glycosylated proteins Human genes 0.000 description 4
- 108091005608 glycosylated proteins Proteins 0.000 description 4
- 239000001307 helium Substances 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- 238000004949 mass spectrometry Methods 0.000 description 4
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 201000010099 disease Diseases 0.000 description 3
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 230000013595 glycosylation Effects 0.000 description 3
- 238000006206 glycosylation reaction Methods 0.000 description 3
- 102000004169 proteins and genes Human genes 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- SHZGCJCMOBCMKK-UHFFFAOYSA-N D-mannomethylose Natural products CC1OC(O)C(O)C(O)C1O SHZGCJCMOBCMKK-UHFFFAOYSA-N 0.000 description 2
- SHZGCJCMOBCMKK-DHVFOXMCSA-N L-fucopyranose Chemical compound C[C@@H]1OC(O)[C@@H](O)[C@H](O)[C@@H]1O SHZGCJCMOBCMKK-DHVFOXMCSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000008827 biological function Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 102000004196 processed proteins & peptides Human genes 0.000 description 2
- 108090000765 processed proteins & peptides Proteins 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FHOMNNOYQDOCJQ-VKKIDBQXSA-N (2S,3S)-1,4-bis(sulfanyl)butane-2,3-diol hydrate Chemical compound O.O[C@H](CS)[C@H](O)CS FHOMNNOYQDOCJQ-VKKIDBQXSA-N 0.000 description 1
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- PNNNRSAQSRJVSB-SLPGGIOYSA-N Fucose Natural products C[C@H](O)[C@@H](O)[C@H](O)[C@H](O)C=O PNNNRSAQSRJVSB-SLPGGIOYSA-N 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 108060003951 Immunoglobulin Proteins 0.000 description 1
- PNNNRSAQSRJVSB-UHFFFAOYSA-N L-rhamnose Natural products CC(O)C(O)C(O)C(O)C=O PNNNRSAQSRJVSB-UHFFFAOYSA-N 0.000 description 1
- 108090001090 Lectins Proteins 0.000 description 1
- 102000004856 Lectins Human genes 0.000 description 1
- OVRNDRQMDRJTHS-UHFFFAOYSA-N N-acelyl-D-glucosamine Natural products CC(=O)NC1C(O)OC(CO)C(O)C1O OVRNDRQMDRJTHS-UHFFFAOYSA-N 0.000 description 1
- OVRNDRQMDRJTHS-FMDGEEDCSA-N N-acetyl-beta-D-glucosamine Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O OVRNDRQMDRJTHS-FMDGEEDCSA-N 0.000 description 1
- MBLBDJOUHNCFQT-LXGUWJNJSA-N N-acetylglucosamine Natural products CC(=O)N[C@@H](C=O)[C@@H](O)[C@H](O)[C@H](O)CO MBLBDJOUHNCFQT-LXGUWJNJSA-N 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 102000004142 Trypsin Human genes 0.000 description 1
- 108090000631 Trypsin Proteins 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000090 biomarker Substances 0.000 description 1
- 230000003592 biomimetic effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 230000007969 cellular immunity Effects 0.000 description 1
- 230000007248 cellular mechanism Effects 0.000 description 1
- 239000012612 commercial material Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000022811 deglycosylation Effects 0.000 description 1
- 239000003398 denaturant Substances 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000004727 humoral immunity Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 102000018358 immunoglobulin Human genes 0.000 description 1
- PGLTVOMIXTUURA-UHFFFAOYSA-N iodoacetamide Chemical compound NC(=O)CI PGLTVOMIXTUURA-UHFFFAOYSA-N 0.000 description 1
- 239000002523 lectin Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 229950006780 n-acetylglucosamine Drugs 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 230000004481 post-translational protein modification Effects 0.000 description 1
- 230000002797 proteolythic effect Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000012588 trypsin Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/265—Adsorption chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/30—Partition chromatography
- B01D15/305—Hydrophilic interaction chromatography [HILIC]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/08—Polysaccharides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K1/00—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length
- C07K1/14—Extraction; Separation; Purification
- C07K1/16—Extraction; Separation; Purification by chromatography
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K1/00—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length
- C07K1/14—Extraction; Separation; Purification
- C07K1/16—Extraction; Separation; Purification by chromatography
- C07K1/20—Partition-, reverse-phase or hydrophobic interaction chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/405—Concentrating samples by adsorption or absorption
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/02—Hydrophilization
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
- B01J2220/52—Sorbents specially adapted for preparative chromatography
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Molecular Biology (AREA)
- Medicinal Chemistry (AREA)
- Genetics & Genomics (AREA)
- Biophysics (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
本发明涉及一种掺杂碳点的壳聚糖膜及其制备与应用。具体是采用“一锅法”策略，将壳聚糖和碳点溶解于乙酸溶液中，在液氮下迅速冷冻，然后放置于冷冻干燥机中，通过胺醛缩合反应，得到掺杂碳点的壳聚糖膜材料。该材料中含有大量的亲水基团，如羟基和氨基等，具有良好的亲水性能。该亲水材料的制备简单，仅需要一步反应完成，无需二次修饰，直接可作为亲水相互作用色谱的吸附剂应用于复杂生物样品(人或动物的体液、组织和细胞酶解液等)的糖肽富集。
Description
技术领域
本发明涉及一种掺杂碳点的壳聚糖膜及其制备与应用。具体是采用“一锅法”策略，将壳聚糖和碳点溶解于乙酸溶液中，在液氮下迅速冷冻，然后放置于冷冻干燥机中，通过胺醛缩合反应，得到掺杂碳点的壳聚糖膜材料。该材料中含有大量的亲水基团，如羟基和氨基等，具有良好的亲水性能，可直接作为亲水相互作用色谱的吸附剂，用于复杂生物样品中糖肽的分离富集。
背景技术
蛋白质的糖基化是一种普遍的蛋白质翻译后修饰，参与了几乎所有的生命活动，其与细胞免疫、体液免疫以及多种疾病的发生都有着密切的关系。近年来的研究表明，糖基化蛋白质是许多疾病的生物标志物，糖基化蛋白质的分析与鉴定以及其生物学功能研究已经成为当前关注人类生命健康的热门研究方向(文献1.Ohtsubo K.,et.al.“Glycosylation in cellular mechanisms of health and disease”Cell,2006,126,855-867)。糖基化蛋白质因连接糖链的位置、糖型数目和糖基序列的不同，可携带众多的生物信息，具有更多生物功能。因此，对糖基化蛋白质的分析具有重要的理论和现实意义。在“鸟枪法”策略中，质谱分析是最重要的研究手段，而糖肽在蛋白质酶解液中的丰度很低，动态分布范围广，直接分析具有很大的挑战，因此在质谱分析前有必要进行富集。目前，已经发展出了多种糖肽富集的方法，主要包括：凝集素亲和法、亲水相互作用色谱法、酰肼化学法和硼酸亲和法等(文献2.Zhang L.W.,et.al.“Facile fabrication of biomimeticchitosan membrane with honeycomb-like structure for enrichment ofglycosylated peptides”Anal.Chem.2019,91,2985-2993；文献3.江静,等.“亲水相互作用色谱结合串联质谱多重碎裂模式在完整糖肽研究中的应用”分析化学，2014,2,159-165)。其中亲水相互作用色谱法可对生物样品中的糖肽进行无差别式富集，同时在富集分析过程中无化学反应发生，操作简单，可重复性强且与质谱高度兼容，因此得到了广泛的应用。
目前已报道的亲水材料有很多，例如亲水化的有机硅杂化整体材料、二氧化硅微球、聚丙烯酰胺微球等(文献4.杨铎,等.“基于巯基-烯烃点击化学的聚丙烯酰胺型亲水作用色谱固定相的制备”分析化学,2015,43,1439-1444；文献5.Liang Y,et al.“Goldnanoparticles immobilized hydrophilic monoliths with variable functionalmodification for highly selective enrichment and on-line deglycosylation ofglycopeptides”Analytica Chimica Acta,2015,900,83-89)。这些材料通常是经过二次修饰来增强材料的亲水性能，制备过程复杂。
发明内容
本发明的目的在于提供一种具有亲水性能的掺杂碳点的壳聚糖膜材料，其可直接作为亲水相互作用色谱的吸附剂，用于复杂生物样品中糖肽的分离富集。
为实现上述目的，可按如下步骤操作：
(1)碳点的制备：加入15～50mL(优选25～35mL)的无水乙醇和10～30mL(优选15～20mL)戊二醛于反应釜中，120～180℃(优选140～150℃)条件下反应2～5h(优选2～3h)合成戊二醛碳点；将得到的戊二醛碳点溶液在45～60℃(优选45～50℃)下，旋转蒸发除去溶剂，得到戊二醛碳点；
(2)掺杂碳点的壳聚糖膜的制备：将50～500mg(优选300～400mg)壳聚糖分散于10～50mL(优选30～40mL)水中，在50～150r/min(优选60～80r/min)的转速下，进行机械搅拌2～8min(优选3～5min)；然后加入100～500μL(优选200～350μL)乙酸，继续搅拌使其形成澄清均一溶液；接着加入步骤(1)中所得到的碳点10～500mg(优选30～100mg)，继续搅拌10～25min(优选12～15min)后，将溶液转移至平底(内部底面为平面)的金属模具中，于液氮中冷冻5～25min(优选15～20min)使溶液完全冷冻成固体，最后将其置于温度为-45～-55℃的冷冻干燥机中(真空度低于20Pa)16～24h，以去除溶剂，得到掺杂碳点的壳聚糖膜。
所制备掺杂碳点的壳聚糖膜可作为亲水相互作用色谱的吸附剂，用于复杂生物样品中糖肽的分离富集。
该材料中含有大量的亲水基团，如羟基和氨基等，具有良好的亲水性能。该亲水材料的制备简单，仅需要一步反应完成，无需二次修饰，直接可作为亲水相互作用色谱的吸附剂应用于复杂生物样品(人或动物的体液、组织和细胞酶解液等)的糖肽富集。
本发明具有如下优点：
(1)该方法制备过程简单，仅经一步反应即可得到具有良好亲水性能的壳聚糖膜材料。
(2)所制备的亲水膜材料，具有的大孔结构有利于快速传质，且不需要二次修饰即可直接作为亲水相互作用色谱的吸附剂，用于复杂生物样品中糖肽的高效富集。
附图说明
图1为掺杂碳点的壳聚糖膜的制备示意图。
图2为壳聚糖膜及其制备单体的傅里叶变换-红外光谱对比图。
图3为壳聚糖膜的外观图以及其表面和横截面的氦离子扫描电镜图；图3a-c为实施例1制备的掺杂碳点的壳聚糖膜(Ⅰ)；图3d-f为实施例2制备的掺杂碳点的壳聚糖膜(Ⅱ)；图3g-i为实施例3制备的未掺杂碳点的壳聚糖膜。
图4为人免疫球蛋白酶解液富集前后的质谱对比图；图4a为富集前酶解液的质谱图；图4b为采用实施例1制备的掺杂碳点的壳聚糖膜(Ⅰ)为吸附剂富集后的质谱图；图4c为采用实施例2制备的掺杂碳点的壳聚糖膜(Ⅱ)为吸附剂富集后的质谱图；图4d为采用商品化吸附材料为吸附剂富集后的质谱图；图中圆点(·)代表鉴定到的糖肽信号。
具体实施方式
实施例1：掺杂碳点的壳聚糖膜材料的制备及应用：
掺杂碳点的壳聚糖膜材料的制备：
(1)碳点的制备：依次加入30mL的无水乙醇和15mL戊二醛于反应釜中，150℃反应2h合成戊二醛碳点；将得到的碳点溶液转移至圆底烧瓶中，45℃条件下旋转蒸发除去溶剂，得到戊二醛碳点；
(2)掺杂碳点的壳聚糖膜(Ⅰ)的制备：在圆底烧瓶中，将350mg壳聚糖分散于35mL水中，然后在70r/min的转速下进行机械搅拌5min，再加入350μL乙酸，搅拌至溶液澄清透明；接着加入步骤(1)中得到的碳点35mg，继续搅拌15min使溶液混合均匀，然后将其转移至平底的铜盘模具中，在液氮中冷冻20min；待其完全冷冻后，置于-45℃冷冻干燥机(真空度低于20Pa)中20h去除溶剂，得到掺杂碳点的壳聚糖膜(Ⅰ)。掺杂碳点的壳聚糖膜的应用：
人免疫球蛋白G(IgG)酶解液的制备：将2.0mg的IgG溶解于1.0mL含有8M的尿素和100mM NH4HCO3的变性剂水溶液中；然后加入20μL浓度为1M二硫苏糖醇水溶液，8000r/min离心20min后，在37℃恒温2h；在避光状态下继续加入7.4mg碘代乙酰胺，避光反应35min；取出后，加入7.0mL的Tris-HCl缓冲液，将尿素浓度稀释为1M；按照酶与蛋白质量比为1：25加入胰蛋白酶，在37℃的水浴中反应18h，获得的酶解液进行除盐，冻干后保存在-20℃的冰箱中备用。
掺杂碳点的壳聚糖膜对于人免疫球蛋白G酶解液中糖肽的富集：首先，将制备好的膜材料剪成长方形片状(长：0.5～1.0cm；宽：0.2～0.5cm，约1mg)至于离心管中；然后，分别用200μL上样溶液(ACN/H2O/TFA，83/16/1，v/v/v)在室温下平衡材料2次，每次15min离心弃去上清液；平衡材料后，将200μL含有10μg IgG酶解液的上样溶液(ACN/H2O/TFA，83/16/1，v/v/v)加入材料中，震荡30min后离心，除去上清液；之后分别用上述上样溶液200μL进行非特异性洗脱两次，每次15min，除去非糖肽；最后用100μL洗脱溶液(ACN/H2O/TFA，30/69/1，v/v/v)进行特异性洗脱，震荡15min离心后取上清液(糖肽富集液)用MALDI TOF 5800质谱，进行基质辅助激光解吸电离飞行时间质谱(MALDI-TOF/MS)分析。
产物表征
壳聚糖膜及其单体的红外表征结果如图2所示。在碳点谱图中出现的波数为1719cm-1处的醛基特征峰(C＝O键伸缩振动峰)，同时出现在了掺杂碳点的壳聚糖膜的谱图中，而没有出现在不掺杂碳点的壳聚糖膜谱图中。在壳聚糖单体谱图中，波数为3356cm-1和3288cm-1分别归属于-OH和-NH2的伸缩振动吸收峰，这些信号也出现在碳点掺杂壳聚糖膜的谱图中。另外在掺杂碳点的壳聚糖膜谱图中，在波数为1632cm-1处出现了C＝N伸缩振动峰，该峰的出现表明戊二醛碳点中的醛基与壳聚糖单体中的氨基发生了胺醛缩合反应。这些结果说明了掺杂碳点的壳聚糖膜是由碳点与壳聚糖单体通过胺醛缩合反应而制得的。
如图3a所示，制备的掺杂碳点的壳聚糖膜(Ⅰ)的外观呈浅红色，冻干后有裂纹；其氦离子扫描电镜结果如图3b-c所示，图中可以清晰看到膜材料表面含有网状大孔(图3b)，横截面呈现出类似蜂窝状的有序大孔结构(图3c)；该材料的孔径50～150μm，孔隙率约为88％；该材料用手触摸，质地较柔软。
产物应用
采用人免疫球蛋白G酶解液为样品，评价材料的糖肽富集性能。图4为IgG酶解液富集前后的MALDI-TOF/MS分析对比图。如图4a所示，富集前的酶解液质谱图中较高的信号峰均为非糖肽信号峰，糖肽的信号几乎观察不到。而使用掺杂碳点的壳聚糖膜(Ⅰ)进行富集后，质谱图中非糖肽信号峰基本消失，糖肽信号明显增强(图4b)。在信噪比为10时，可检测到20条N-糖肽的信号(表1)。该结果表明本实施例制备的掺杂碳点的壳聚糖膜(Ⅰ)对糖肽具有非常良好的富集效率与选择性。
表1掺杂碳点的壳聚糖膜(Ⅰ)富集到的IgG酶解液中糖肽的质荷比及糖型组成
N#表示糖基化位点；Hex:甘露糖；HexNAc:N-乙酰葡糖胺；Fuc:岩藻糖。
实施例2：掺杂碳点的壳聚糖膜(Ⅱ)的制备及应用：
(1)掺杂碳点的壳聚糖膜(Ⅱ)的制备：制备过程和条件同实施例1，与实施例1不同之处在于，制备过程中反应液中碳点加入量提高到70mg，其它过程同实施例1。
(2)掺杂碳点的壳聚糖膜(Ⅱ)应用于酶解液中糖肽的分离富集：富集实验过程和方法同实施例1。
产物表征
掺杂碳点的壳聚糖膜(Ⅱ)的外观如图3d所示，膜材料显暗红色，与实施例1中得到的壳聚糖膜(I)颜色略有不同；氦离子扫描电镜图显示，该膜表面也含有孔，但是非常致密(图3e)，其横截面也呈规则的类似蜂窝状的孔道结构(图3f)；该材料孔径范围50～150μm，孔隙率约为82％，低于实施例1制备的膜材料的对应值；用手触摸，质地较硬，比实施例1中得到的膜(I)材料硬度要高，这可能是因为碳点作为交联剂时，反应液中其含量越高，交联度越大。
产物应用
使用该膜材料作为吸附剂，对人免疫球蛋白G酶解液中的糖肽进行富集，结果如图4c所示，质谱图中非糖肽信号基本消失，糖肽信号很强。在信噪比为10时，可检测到15条典型的N-糖肽(表2)。该结果表明，该材料对酶解液中的糖肽也具有良好的选择性与富集效率，但与实施例1中的富集结果相比，富集到的糖肽信号值和数量均偏低，这可能是因为反应液中碳点含量的增加，虽可以增加合成膜的硬度，但其亲水性不及壳聚糖，从而导致合成膜的亲水性下降，对于糖肽的富集效率降低。
表2掺杂碳点的壳聚糖膜(Ⅱ)富集到的IgG酶解液中糖肽的质荷比及糖型组成
实施例3：未掺杂碳点的壳聚糖膜的制备及应用：
(1)壳聚糖膜材料的制备：制备过程和条件同实施例1，与实施例1不同之处在于，反应液中不加入碳点，其它过程同实施例1。
(2)壳聚糖膜材料应用于糖肽分离富集，实验过程和方法同实施例1。
产物表征
所制备的未掺杂碳点的壳聚糖膜材料的红外表征结果如图2所示，纯壳聚糖膜与壳聚糖单体的谱图中均存在-OH(3356cm-1)和-NH2(3288cm-1)的特征伸缩振动吸收峰。壳聚糖单体经交联成膜后，由于氢键作用增强，位于1556cm-1及1405cm-1处的C-N键变形振动吸收峰信号明显增强，说明该膜由壳聚糖单体自聚交联而成。
得到的壳聚糖膜的外观如图3g所示，膜呈乳白色，明显不同于实施例1和2中得到的红色膜；氦离子扫描电镜图显示，该材料也具有大孔结构(图3h-i)；孔径范围10～50μm，孔隙率约为89％；用手触摸，质地很软，比实施例1和2中得到的膜材料硬度都低，进一步说明了碳点的加入可以提高合成膜的强度。
产物应用
实验中发现不掺杂碳点的壳聚糖膜材料在酸性溶液中极易溶解，即使平衡溶液中三氟乙酸的含量仅有1％(v％)，平衡30min后，壳聚糖膜已经在溶液中发生溶解，无法进行后续的富集过程，不能应用于糖肽富集。
对比例：商品化亲水材料应用于糖肽分离富集：
为了进行对比，从博纳艾杰尔科技有限公司购买了商品化亲水材料(VenusilHILIC，10μm)，使用与实施例1中相同的步骤对人免疫球蛋白G酶解液中的糖肽进行富集。结果显示(图4d)，该材料作为吸附剂时，虽然可富集到21条糖肽(表3所示，信噪比为10)，但谱图信号值偏低，非糖肽信号不可忽视，说明其对糖肽的选择较差。与实施例1和2的结果对比，掺杂碳点的壳聚糖膜对糖肽具有更高的选择性。
表3商品化材料富集到的IgG酶解液中糖肽的质荷比及糖型组成
以上结果表明，本发明以戊二醛碳点为交联剂制备的掺杂碳点的壳聚糖膜，具有有序的大孔结构以及良好的亲水性。作为亲水富集材料，对糖肽具有优异的富集效率和选择性，可用于复杂生物样品中糖肽的高效富集。
Claims (7)
1.一种掺杂碳点的壳聚糖膜的制备方法，该材料由壳聚糖和戊二醛碳点，通过氨醛缩合反应一步制备而成；其制备可按如下步骤进行：
（1）碳点的制备：加入15~50 mL的无水乙醇和10~30 mL戊二醛于反应釜中，120~180 ℃条件下反应2~5 h合成戊二醛碳点；将得到的戊二醛碳点溶液在45~60℃下，旋转蒸发除去溶剂，得到戊二醛碳点；
（2）掺杂碳点的壳聚糖膜的制备：将50~500 mg壳聚糖分散于10~50 mL水中，在50~150r/min的转速下，进行机械搅拌2~8 min；然后加入100~500 μL乙酸，继续搅拌使其形成澄清均一溶液；接着加入步骤（1）中所得到的碳点10~500 mg，继续搅拌10~25 min后，将溶液转移至平底的模具中，于液氮中冷冻5~25 min使溶液完全冷冻成固体，最后将其冷冻干燥，以去除溶剂，得到掺杂碳点的壳聚糖膜。
2.根据权利要求1所述的制备方法，其特征在于：
步骤（1）中碳点的制备：加入25~35 mL的无水乙醇和15~20 mL戊二醛于反应釜中， 140~150 ℃条件下反应2~3 h合成戊二醛碳点；将得到的戊二醛碳点溶液在45~50 ℃下，旋转蒸发除去溶剂，得到戊二醛碳点；
步骤（2）中掺杂碳点的壳聚糖膜的制备：将300~400 mg壳聚糖分散于 30~40 mL水中，在60~80 r/min的转速下，进行机械搅拌3~5 min；然后加入200~350 μL乙酸，继续搅拌使其形成澄清均一溶液；接着加入步骤（1）中所得到的碳点30~100 mg，继续搅拌12~15 min后，将溶液转移至平底的模具中，于液氮中冷冻15~20 min使溶液完全冷冻成固体，最后将其冷冻干燥，以去除溶剂，得到掺杂碳点的壳聚糖膜。
3.根据权利要求1所述的制备方法，其特征在于：于冷冻干燥机中进行冷冻干燥，冷冻干燥时间16~24 h，冷冻干燥温度条件为-45~-55℃，真空度低于20 Pa。
4.一种权利要求1~3任一所述方法制备获得的掺杂碳点的壳聚糖膜。
5.一种权利要求4所述掺杂碳点的壳聚糖膜的应用，其作为亲水相互作用色谱的吸附剂或填料。
6.根据权利要求4所述掺杂碳点的壳聚糖膜的应用，其特征在于：该材料具有良好的亲水性能，直接作为亲水相互作用色谱的吸附剂或填料，用于生物样品中的糖肽富集。
7.根据权利要求6所述的应用，其特征在于：所述的生物样品为人体和/或动物的体液、组织以及细胞酶解液中的一种或二种以上。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110234611.2A CN115007113B (zh) | 2021-03-03 | 2021-03-03 | 一种掺杂碳点的壳聚糖膜及其制备与应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110234611.2A CN115007113B (zh) | 2021-03-03 | 2021-03-03 | 一种掺杂碳点的壳聚糖膜及其制备与应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115007113A CN115007113A (zh) | 2022-09-06 |
| CN115007113B true CN115007113B (zh) | 2024-04-23 |
Family
ID=83064761
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110234611.2A Active CN115007113B (zh) | 2021-03-03 | 2021-03-03 | 一种掺杂碳点的壳聚糖膜及其制备与应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115007113B (zh) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108645903A (zh) * | 2018-01-17 | 2018-10-12 | 江苏大学 | 基于碳点-壳聚糖修饰玻碳电极的分子印迹传感器的制备及应用 |
| CN110961083A (zh) * | 2018-09-29 | 2020-04-07 | 中国科学院大连化学物理研究所 | 一种亲水性壳聚糖整体材料及其制备和应用 |
| CN111208090A (zh) * | 2020-03-11 | 2020-05-29 | 广州市加和检测技术服务有限公司 | 一种利用壳聚糖碳点检测重金属离子的spr传感器和芯片 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11161094B2 (en) * | 2019-05-01 | 2021-11-02 | Imam Abdulrahman Bin Faisal University | Titania-carbon dot-reduced graphene oxide composites, their make, and use |
-
2021
- 2021-03-03 CN CN202110234611.2A patent/CN115007113B/zh active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108645903A (zh) * | 2018-01-17 | 2018-10-12 | 江苏大学 | 基于碳点-壳聚糖修饰玻碳电极的分子印迹传感器的制备及应用 |
| CN110961083A (zh) * | 2018-09-29 | 2020-04-07 | 中国科学院大连化学物理研究所 | 一种亲水性壳聚糖整体材料及其制备和应用 |
| CN111208090A (zh) * | 2020-03-11 | 2020-05-29 | 广州市加和检测技术服务有限公司 | 一种利用壳聚糖碳点检测重金属离子的spr传感器和芯片 |
Non-Patent Citations (1)
| Title |
|---|
| Fluorescent Self-Healing Carbon Dot/Polymer Gels;Sagarika Bhattacharya et al.;《ACS Nano》;第Vol. 13卷;第1440页结论和左栏第4段 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115007113A (zh) | 2022-09-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108906007B (zh) | 一种糖基亲水磁性复合物微球的制备方法及其应用 | |
| CN103364494B (zh) | 一种对血清糖肽组高选择性富集的方法 | |
| CN110152624A (zh) | 一种微孔聚合物包覆的亲水性树脂及其在糖肽富集中的应用 | |
| CN109942667A (zh) | 二维金属有机骨架纳米片富集磷酸化肽段的方法和应用 | |
| Li et al. | Porous graphene oxide/chitosan beads with honeycomb-biomimetic microchannels as hydrophilic adsorbent for the selective capture of glycopeptides | |
| CN113721028B (zh) | 一种go@cs@zif-8泡沫材料的合成方法及应用 | |
| CN115007113B (zh) | 一种掺杂碳点的壳聚糖膜及其制备与应用 | |
| CN106732464B (zh) | 一种亲水树枝和c18修饰的磁性石墨烯材料及其制备方法和应用 | |
| Li et al. | Coupling of metal-organic frameworks-containing monolithic capillary-based selective enrichment with matrix-assisted laser desorption ionization-time-of-flight mass spectrometry for efficient analysis of protein phosphorylation | |
| CN110961083B (zh) | 一种亲水性壳聚糖整体材料及其制备和应用 | |
| CN110575825B (zh) | 一种磷酸功能化和Ti-IMAC碳材料及其制备和应用 | |
| CN116813920A (zh) | β-环糊精功能化共价有机骨架复合材料的制备方法及应用 | |
| CN107478839A (zh) | 赖氨酸氮连接磷酸化翻译后修饰富集和鉴定的方法 | |
| CN112147210A (zh) | 一种硼酸功能化介孔石墨烯-二氧化硅复合材料的制备方法、产品及应用 | |
| CN112844258A (zh) | 一种半胱氨酸修饰的纳米核壳硅胶材料及制备与应用 | |
| CN109012611A (zh) | 一种纤维素微球、纤维素微柱及其制备方法和应用 | |
| CN115869925A (zh) | 一种聚合物微球及基于反相悬浮聚合法的制备和其应用 | |
| Liu et al. | A rapid approach for fabricating boronic acid-functionalized plates for on-probe detection of glycoprotein and glycopeptide | |
| CN113318480B (zh) | 一种亲水性纳米核壳材料及其制备方法和应用 | |
| CN115212852B (zh) | 一种亲水膜层包覆的大孔树脂材料及其制备和应用 | |
| CN110872383B (zh) | 一种青霉胺修饰的多级孔杂化材料的制备及其应用 | |
| CN115245813B (zh) | 一种复合微球及其制备和在磷酸化肽吸附中的应用 | |
| CN113150062B (zh) | 一种特异性分离富集内源性糖基化肽的方法 | |
| CN115124722B (zh) | 磁性胍基功能化共价有机骨架复合材料及其制备方法和应用 | |
| CN115007119A (zh) | 一种含有两性离子的亲水微球及其制备和应用 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |