CN116493599A - 一种银纳米立方的制备方法 - Google Patents
一种银纳米立方的制备方法 Download PDFInfo
- Publication number
- CN116493599A CN116493599A CN202310452569.0A CN202310452569A CN116493599A CN 116493599 A CN116493599 A CN 116493599A CN 202310452569 A CN202310452569 A CN 202310452569A CN 116493599 A CN116493599 A CN 116493599A
- Authority
- CN
- China
- Prior art keywords
- silver
- penetrating peptide
- nanocubes
- cell
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229910052709 silver Inorganic materials 0.000 claims abstract description 43
- 239000004332 silver Substances 0.000 claims abstract description 43
- 108010051109 Cell-Penetrating Peptides Proteins 0.000 claims abstract description 29
- 102000020313 Cell-Penetrating Peptides Human genes 0.000 claims abstract description 29
- 239000000243 solution Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 108090000765 processed proteins & peptides Proteins 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 125000002091 cationic group Chemical group 0.000 claims abstract description 10
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000004321 preservation Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000000149 penetrating effect Effects 0.000 claims abstract description 7
- 210000000170 cell membrane Anatomy 0.000 claims abstract description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 5
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- 230000002378 acidificating effect Effects 0.000 claims abstract description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 27
- 101710085003 Alpha-tubulin N-acetyltransferase Proteins 0.000 claims description 24
- 101710085461 Alpha-tubulin N-acetyltransferase 1 Proteins 0.000 claims description 24
- 101710175714 Tyrosine aminotransferase Proteins 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 11
- 238000011534 incubation Methods 0.000 claims description 5
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 4
- 229940071536 silver acetate Drugs 0.000 claims description 4
- 239000003002 pH adjusting agent Substances 0.000 claims description 3
- 108010043655 penetratin Proteins 0.000 claims description 3
- MCYTYTUNNNZWOK-LCLOTLQISA-N penetratin Chemical compound C([C@H](NC(=O)[C@H](CC=1C2=CC=CC=C2NC=1)NC(=O)[C@H]([C@@H](C)CC)NC(=O)[C@H](CCCCN)NC(=O)[C@@H](NC(=O)[C@H](CCC(N)=O)NC(=O)[C@@H](N)CCCNC(N)=N)[C@@H](C)CC)C(=O)N[C@@H](CCC(N)=O)C(=O)N[C@@H](CC(N)=O)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](CCSC)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CCCCN)C(N)=O)C1=CC=CC=C1 MCYTYTUNNNZWOK-LCLOTLQISA-N 0.000 claims description 3
- 229920000724 poly(L-arginine) polymer Polymers 0.000 claims description 3
- 108010011110 polyarginine Proteins 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- -1 silver ions Chemical class 0.000 abstract description 6
- 210000004027 cell Anatomy 0.000 abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 10
- 239000013078 crystal Substances 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 6
- 102000003992 Peroxidases Human genes 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000012010 growth Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 108040007629 peroxidase activity proteins Proteins 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 101710134784 Agnoprotein Proteins 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 description 2
- 239000004475 Arginine Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 description 1
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 description 1
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- AVKUERGKIZMTKX-NJBDSQKTSA-N ampicillin Chemical compound C1([C@@H](N)C(=O)N[C@H]2[C@H]3SC([C@@H](N3C2=O)C(O)=O)(C)C)=CC=CC=C1 AVKUERGKIZMTKX-NJBDSQKTSA-N 0.000 description 1
- 229960000723 ampicillin Drugs 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- BHONFOAYRQZPKZ-LCLOTLQISA-N chembl269478 Chemical compound C([C@H](NC(=O)[C@H](CC=1C2=CC=CC=C2NC=1)NC(=O)[C@H]([C@@H](C)CC)NC(=O)[C@H](CCCCN)NC(=O)[C@@H](NC(=O)[C@H](CCC(N)=O)NC(=O)[C@@H](N)CCCNC(N)=N)[C@@H](C)CC)C(=O)N[C@@H](CCC(N)=O)C(=O)N[C@@H](CC(N)=O)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](CCSC)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CCCCN)C(O)=O)C1=CC=CC=C1 BHONFOAYRQZPKZ-LCLOTLQISA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002091 nanocage Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 238000012634 optical imaging Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 238000004917 polyol method Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000035040 seed growth Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000007974 sodium acetate buffer Substances 0.000 description 1
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
- B22F2009/245—Reduction reaction in an Ionic Liquid [IL]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/25—Noble metals, i.e. Ag Au, Ir, Os, Pd, Pt, Rh, Ru
- B22F2301/255—Silver or gold
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Peptides Or Proteins (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
本发明公开了一种银纳米立方的制备方法,包括以下步骤:(1)将阳离子型细胞穿膜肽加入水中,搅拌至完全溶解,配制成细胞穿膜肽水溶液,呈酸性,然后继续搅拌条件下,滴加碱性pH调节试剂,调节溶液pH值至碱性;(2)在持续搅拌步骤(1)制备的细胞穿膜肽水溶液条件下,缓慢滴加可溶性银盐溶液,保温反应,得到银纳米立方体;该方法基于细胞穿膜肽对银离子的配位作用和自还原作用,可以在较温和的反应条件,不需要额外添加还原剂以及目前合成银纳米立方体方法普遍使用的各种有机试剂,合成银纳米立方。
Description
技术领域
本发明涉及一种银纳米颗粒的制备方法,特别涉及一种银纳米立方的制备方法。
背景技术
随着对金属纳米结构的研究不断深入,研究者逐渐能够精确控制纳米级金属的制备与生产,通过微调其性能进一步开发新兴应用。而金属纳米结构的光学和磁性不仅高度依赖于其尺寸,还取决于形状。在众多金属中,银是纳米结构研究最多的材料之一,这与其在等离子体和表面增强拉曼散射(SERS)等应用中具有的卓越性能息息相关,也是执行高灵敏度检测的理想材料。此前,一系列不同形貌的银纳米结构已经被合成出来,包括球体、圆盘状、三角片状、棒状、线状、棱镜状、右双锥体和立方体等等。而其中银纳米立方体的研究受到了极大关注,银纳米立方体可以作为牺牲模板,通过与氯金酸的电替代反应产生具有可调共振峰的金纳米笼,在增强光学成像对比度和光热处理效果等生物医学应用中具有很大的前景。银纳米颗粒的特定光学特征与其颗粒大小、形状密切相关,而立方体结构的银纳米颗粒较之其他形状,有效表面积得到提升,具有更强的催化潜力。此外,与纳米球相比,纳米立方体对大肠杆菌和金黄色葡萄球菌均表现出更高的抗菌活性,与抗生素氨苄青霉素的协同作用也很有前景。
此前,已有较成熟的制备银纳米立方体方案。最早在2002年,Yugang Sun和YounanXia就在聚乙烯吡咯烷酮(PVP)存在下,利用乙二醇还原硝酸银,合成银纳米立方颗粒(《Shape-Controlled Synthesis of Gold and Silver Nanoparticles》,Science,2010,298(10):2176-2179),其研究结果表明,产物的形貌受温度、AgNO3浓度、PVP和AgNO3单位摩尔比等反应条件的影响较大。此后,纳米立方银的合成多采用多元醇工艺,在有机相中进行控制反应来合成。例如,Im.S.H等人在聚乙烯吡咯烷酮(PVP)和HCl的存在下,140℃下利用乙二醇还原硝酸银,合成均匀的纳米立方体银(《Large-scale synthesis of silvernanocubes:the role of HCl in promoting cube perfection and monodispersity》,Angew.Chem.,Int.Ed.2005,44,2154–2157);Andrea Tao等人以硝酸银为前体、PVP为封端剂控制形状、戊二醇为溶剂和还原剂制备银纳米立方体,实验发现极少量的氯离子使AgCl的溶解度降低并析出,阻止了银离子的快速还原,最终导致银立方体的产生(《Polyhedralsilver nanocrystals with distinct scattering signatures》,Angew.Chem.,Int.Ed.2006,45(28),4597–4601)。
但是,上述银纳米立方体的制备都是在较高温度、有机溶剂多元醇环境下制备,制得的产物还需进行分离、洗涤等处理,工艺复杂,成本较高。
发明内容
发明目的:本发明旨在提供一种不使用有机多元醇、反应条件温和工艺简单的银纳米立方的制备方法。
技术方案:本发明的银纳米立方的制备方法,包括以下步骤:
(1)将阳离子型细胞穿膜肽加入水中,搅拌至完全溶解,配制成细胞穿膜肽水溶液,呈酸性,然后继续搅拌条件下,滴加碱性pH调节试剂,调节溶液pH值至碱性;
(2)在持续搅拌步骤(1)制备的细胞穿膜肽水溶液条件下,缓慢滴加可溶性银盐溶液,保温反应,得到银纳米立方体。
步骤(2)中,保温反应过程溶液由无色变为黄绿色。优选的,步骤(2)中,所述保温反应温度为30~40℃,保温时长为8~72小时。
优选的,步骤(1)中,所述阳离子型细胞穿膜肽为TAT(CCYRGRKKRRQRRR)、Penetratin(RQIKIWFQNRRMKWKK)或Polyarginine(R12)。阳离子型细胞穿膜肽TAT、Penetratin和Polyarginine均购于上海强耀生物科技有限公司。
优选的,步骤(1)中,所述调节溶液pH值至碱性的pH为9~12。
优选的,步骤(2)中,所述细胞穿膜肽与银盐中Ag+的摩尔比为1:20~30。细胞穿膜肽比例提高时,合成银立方尺寸减小;Ag+比例提高时,合成银立方尺寸增大。
优选的,步骤(1)中,所述细胞穿膜肽溶液中细胞穿膜肽的浓度为0.053mM~0.106mM。
优选的,步骤(2)中,所述可溶性银盐溶液中的Ag+浓度为1.25mM~1.8544mM。
优选的,步骤(2)中,所述可溶性银盐为硝酸银或乙酸银。
所述银纳米立方体内部为立方体银核,表面为细胞穿肽膜;所述银纳米立方体边长为50~200nm。
优选的,步骤(1)中,所述碱性pH调节试剂是指NaOH、KOH或氨水。
发明机理:阳离子型细胞穿膜肽(如TAT型细胞穿膜肽)由富含精氨酸、赖氨酸和组氨酸的短肽组成,其可以与Ag+发生相互作用,吸附到的Ag+特定晶面上,而其本身所具有的还原性基团能够在适当调节下将Ag+还原成银原子,进而长大成银纳米颗粒;由于细胞穿膜肽吸附在银颗粒的特定晶面表面,会从而限制Ag颗粒向某些晶面的生长速度,并最终使其生长为由细胞穿膜肽所保护的纳米立方体稳定结构。
有益效果:与现有技术相比,本发明具有如下显著优点:(1)该方法基于细胞穿膜肽对银离子的配位作用和自还原作用,可以在较温和的反应条件,不需要额外添加还原剂以及目前合成银纳米立方体方法普遍使用的各种有机试剂,合成银纳米立方;(2)该方法具有低碳环保、安全可靠、方法简单,经济性好等多重优势;(3)该方法合成的银纳米立方体还具有良好的过氧化物酶活性,可用于催化、检测、抗菌、抗肿瘤等用途,显示了材料的功能性效果。
附图说明
图1为实施例1以TAT细胞穿膜肽作为配体合成的银纳米立方的TEM图片;
图2为实施例1制备的银纳米立方的放大的单个银纳米立方体TEM照片;
图3为实施例1制备的银纳米立方的过氧化物酶活性光谱表征图;
图4为实施例1制备的银纳米立方的催化双氧水氧化TMB的显示反应图;
图5为实施例2在实施例1基础上改变浓度和配比制备的银纳米立方的TEM图片;
图6为实施例3在实施例1基础上提高pH值合成的银纳米立方的TEM图片;
图7为实施例4在实施例1基础上改变反应温度合成的银纳米立方的边长分布统计图;
图8为实施例5在实施例1基础上延迟保温时间合成的银纳米立方的TEM明场和暗场图片;
图9为对比例2在有机相DMF中合成银纳米颗粒的TEM图片。
具体实施方式
下面结合实施例对本发明的技术方案作进一步说明。
实施例1
(1)将TAT细胞穿膜肽加入去离子水中,持续搅拌直至完全溶解,配制成浓度为0.053mM的TAT细胞穿膜肽水溶液,该溶液呈酸性;在持续搅拌上述TAT细胞穿膜肽水溶液的条件下,缓缓滴加NaOH溶液调节反应溶液的pH值至9;
(2)配制浓度为1.25mM硝酸银水溶液待用;
(3)在持续搅拌TAT细胞穿膜肽溶液的条件下,按TAT:Ag+摩尔比1:20的比例,将硝酸银溶液向TAT细胞穿膜肽水溶液中缓慢滴加,直到全部滴加结束,30℃保温反应24h后得到合成材料。
通过透射电镜表征合成的材料,结果见图1和图2。由图1可得,制备的银纳米颗粒为银纳米立方体结构,边长尺寸主要分布在50nm~100nm范围内。由图2可得,银纳米立方内部是立方体银核,表面为TAT细胞穿膜肽配体。
为检验合成的银纳米立方体是否具有过氧化物纳米酶活性,分别配置了(Ⅰ)10mMTMB溶液,(Ⅱ)10mM H2O2溶液,(Ⅲ)10mM TMB和10mM H2O2混合溶液,(Ⅳ)0.075mM银纳米立方、10mM TMB和10mM H2O2混合溶液,并用乙酸-乙酸钠缓冲溶液调节体系pH值为4,室温反应3小时后测量其在500~800nm的紫外-可见光光谱。测试结果见图3和4。
图3为实施例1制备的银纳米立方的过氧化物酶活性光谱表征图。由图3可得,Ⅰ、Ⅱ、Ⅲ号溶液放置3小时后均未出现特征吸收峰,只有同时含有银纳米立方、TMB和H2O2的缓冲溶液在反应3小时后在652nm处出现明显吸收峰,此处为TMB氧化物oxTMB的特征吸收峰。
图4为实施例1制备的银纳米立方的催化双氧水氧化TMB的显示反应图。图4可得,oxTMB的特征吸收峰的出现及溶液变蓝,进一步证实了所制得的银纳米立方能够催化H2O2氧化还原态底物TMB,具有过氧化物酶催化活性。
实施例2
在实施例1的基础上,TAT水溶液的浓度为0.106mM,硝酸银水溶液的浓度为1.8544mM,TAT:Ag+摩尔比为1:30,其余条件不变。
图5为该实施例制备的银纳米立方体的TEM照片,由图5可知,其边长尺寸为100~150nm,表明改变浓度和配比可以改变合成银纳米立方体的边长尺寸,但不影响其形状。说明可以通过调节浓度和配比对水相银纳米立方尺寸进行调控,TAT量一定的情况下,提高反应物中Ag+的配比量,有利于生长为尺寸更大的银立方。
实施例3
在实施例1的基础上,改变步骤(1)AT细胞穿膜肽溶液的pH为12,其余条件不变。
图6为该实施例制备银纳米立方的TEM照片,结果表明制备的银纳米立方平均边长尺寸为100~120nm,大于实施例1。这可能是由于pH增加会改变穿膜肽构象,及有利促进银纳米立方还原和生长有关。
实施例4
在实施例1的基础上,改变保温反应温度为40℃,其余条件不变。
图7该条件制备的银纳米立方,主要尺寸分布在70~130nm,略大于实施例1。这与一般情况下,提高反应温度,有利于晶粒长大一致。
实施例5
在实施例1的基础上,改变保温反应时间为72h,其余条件不变。
图8该实施例制备银纳米立方的TEM明场和暗场照片,其边长尺约为110nm,相比实施例1,尺寸略大于实施例1。这与一般情况下,保温时间延长有利于晶粒长大一致。
实施例6
在实施例1的基础上,将细胞穿膜肽TAT替换为Penetratin,其余条件不变。
该改变不影响实验结果,制备的银纳米立方结果与实施例1基本一致。
实施例7
在实施例1的基础上,将硝酸银替换为乙酸银,其余条件不变。
该改变对合成结果不产生影响,制备的银纳米立方结果与实施例1基本一致。表明可溶性银盐硝酸银和乙酸银都可用于该方法合成水相银纳米立方。
实施例8
在实施例1的基础上,将氢氧化钠替换为氢氧化钾,其余条件不变。
该改变对合成结果不产生影响,制备的银纳米立方结果与实施例1基本一致。表面NaOH、KOH等都可用于作为该方法中的pH调节试剂。
对比例1
在实施例1的基础上,将TAT水溶液滴加到硝酸银水溶液中,其余条件不变。
未能成功合成出水相银纳米立方体。调换硝酸银和TAT滴加顺序得不到银纳米立方,可能是由于将硝酸银溶液滴加到TAT水溶液时,由于TAT过量,能立刻与银离子配位结合形成良好的特定晶面保护,有利于之后在保温反应中控制其晶种生长为银立方晶体;而将TAT滴入硝酸银溶液中,由于开始滴入时TAT量较少,未能和银离子形成充分的配位保护,因此最终未能限制银晶种长成立方结构。
对比例2
在37℃下,将10mL浓度为4mM的AgNO3 DMF溶液滴入10mL浓度为4mM的TAT穿膜肽DMF溶液中,剧烈搅拌反应72h,得到非立方体形状的银纳米颗粒,经过透析将在DMF溶剂中合成的TAT功能化纳米银转化为水相,合成的银纳米颗粒如图9所示。
由图9可得,以DMF为溶剂,采用TAT穿膜肽为配体和实施例类似的工艺,合成产物却为形状不规则的银纳米颗粒,不能生成银纳米立方,表明穿膜肽在水中才能在银立方合成中发挥其适合配体的作用。
Claims (10)
1.一种银纳米立方的制备方法,其特征在于,包括以下步骤:
(1)将阳离子型细胞穿膜肽加入水中,搅拌至完全溶解,配制成细胞穿膜肽水溶液,呈酸性,然后继续搅拌条件下,滴加碱性pH调节试剂,调节溶液pH值至碱性;
(2)在持续搅拌步骤(1)制备的细胞穿膜肽水溶液条件下,缓慢滴加可溶性银盐溶液,保温反应,得到银纳米立方体。
2.根据权利要求1所述的银纳米立方的制备方法,其特征在于,步骤(2)中,所述保温反应温度为30~40℃,保温时长为8~72小时。
3.根据权利要求1所述的银纳米立方的制备方法,其特征在于,步骤(1)中,所述阳离子型细胞穿膜肽为TAT、Penetratin或Polyarginine。
4.根据权利要求1所述的银纳米立方的制备方法,其特征在于,步骤(1)中,所述调节溶液pH值至碱性的pH为9~12。
5.根据权利要求1所述的银纳米立方的制备方法,其特征在于,步骤(2)中,所述细胞穿膜肽与银盐中Ag+的摩尔比为1:20~30。
6.根据权利要求1所述的银纳米立方的制备方法,其特征在于,步骤(1)中,所述细胞穿膜肽溶液中细胞穿膜肽的浓度为0.053mM~0.106mM。
7.根据权利要求1所述的银纳米立方的制备方法,其特征在于,步骤(2)中,所述可溶性银盐溶液中的Ag+浓度为1.25mM~1.8544mM。
8.根据权利要求1所述的银纳米立方的制备方法,其特征在于,步骤(2)中,所述可溶性银盐为硝酸银或乙酸银。
9.根据权利要求1所述的银纳米立方的制备方法,其特征在于,所述银纳米立方体内部为立方体银核,表面为细胞穿肽膜;所述银纳米立方体边长为50~200nm。
10.根据权利要求1所述的银纳米立方的制备方法,其特征在于,步骤(1)中,所述碱性pH调节试剂是指NaOH、KOH或氨水。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310452569.0A CN116493599A (zh) | 2023-04-25 | 2023-04-25 | 一种银纳米立方的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310452569.0A CN116493599A (zh) | 2023-04-25 | 2023-04-25 | 一种银纳米立方的制备方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN116493599A true CN116493599A (zh) | 2023-07-28 |
Family
ID=87324186
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202310452569.0A Pending CN116493599A (zh) | 2023-04-25 | 2023-04-25 | 一种银纳米立方的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN116493599A (zh) |
-
2023
- 2023-04-25 CN CN202310452569.0A patent/CN116493599A/zh active Pending
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US10981231B2 (en) | Methods for production of silver nanostructures | |
US8529963B2 (en) | Method for preparing dispersions of precious metal nanoparticles and for isolating such nanoparticles from said dispersions | |
EP2632850B1 (en) | Nano wire and method for manufacturing the same | |
US8084140B2 (en) | Silver platelets comprising palladium | |
Yazid et al. | Synthesis and characterization of gold nanoparticles supported on zinc oxide via the deposition-precipitation method | |
KR101842763B1 (ko) | 구리 나노구조물의 제조방법 | |
CN114425055B (zh) | 一种二氧化硅负载多金属纳米颗粒及其制备方法及其抗菌应用 | |
JP4496026B2 (ja) | 金属銅微粒子の製造方法 | |
KR101368404B1 (ko) | 금속 나노입자 및 이의 제조방법 | |
Mourdikoudis et al. | Colloidal chemical bottom-up synthesis routes of pnictogen (As, Sb, Bi) nanostructures with tailored properties and applications: a summary of the state of the art and main insights | |
Choi et al. | Shape-and size-controlled synthesis of noble metal nanoparticles | |
CN116493599A (zh) | 一种银纳米立方的制备方法 | |
CN113118432A (zh) | 贵金属纳米粒子及其制备方法和应用 | |
KR20120045711A (ko) | 구리 나노입자의 제조방법 | |
CN115365510A (zh) | 一种Yolk-Shell结构的双金属多层多孔中空纳米粒子及其合成方法 | |
KR100661621B1 (ko) | 금속 나노 입자가 포함된 콜로이드 및 그 제조방법 | |
KR20090077530A (ko) | 모양 조절이 가능한 금 나노 입자의 합성 방법 | |
Mashayekhi Shams et al. | A study of the influence of percentage of copper on the structural and optical properties of Au-Cu nanoparticle | |
KR101790536B1 (ko) | 표면개질된 산화철, 산화철-귀금속 나노입자 복합체 및 그의 제조방법 | |
CN114523120B (zh) | 一种金属合金纳米簇颗粒的制备方法 | |
Mikhailov | Achievements in the synthesis of elemental silver nanoparticles with various geometric forms | |
Matei et al. | Synthesis of Poly (vinylpyrrolidone) protected Pd-Ag Bimetallic Nanoparticles by Polyol Method | |
JP2019002059A (ja) | 銀粒子の製造方法 | |
KR20210074483A (ko) | 촉매 담지 구조체 및 이의 제조 방법 | |
CN116475425A (zh) | 一种合成金/银核壳结构纳米粒子的方法 |
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 |