CN117282404A - 一种银纳米颗粒功能化共价有机框架微球及其制备和应用 - Google Patents
一种银纳米颗粒功能化共价有机框架微球及其制备和应用 Download PDFInfo
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Abstract
本发明公开了一种银纳米颗粒功能化共价有机框架微球及其富集萃取与比色检测应用。该微球是以亚胺型共价有机框架作为基质,利用其表面巯基或氨基捕获银离子并采用原位还原方式实现银纳米颗粒功能化。制得的银纳米颗粒功能化共价有机框架微球作为分散固相萃取吸附剂或管内固相微萃取吸附剂,利用该微球与不饱和分析物之间的电荷转移作用以及π‑π堆积作用,实现复杂样品中微量不饱和分析物的选择性富集分析。此外,该微球还具有较强的类氧化酶活性和对底物3,3',5,5'‑四甲基联苯胺的高亲和性,基于此构建以该微球作为探针、紫外‑可见分光光度计作为读出装置的简单快速的比色检测法,实现实际生物体液样品中微量多巴胺的高效比色检测。
Description
技术领域
本发明属于共价有机框架复合材料合成与应用技术领域,具体涉及一种银纳米颗粒功能化共价有机框架微球及其制备方法和在富集萃取与比色检测中的应用。
背景技术
共价有机框架(COFs)是一类完全由轻元素通过强共价键组成的结晶性多孔聚合物,具有极高的比表面积、明确的规则孔隙、可调节的功能以及在恶劣介质中的良好稳定性等优点,在如储能、催化、传感、药物分析、样品前处理等诸多领域受到广泛关注。将COFs材料进一步与金属纳米颗粒(MNPs)、金属氧化物(MOS)、金属有机骨架(MOFs)、生物酶等材料相结合,制备COFs基复合材料,可进一步发挥COFs的特殊性能并且拓展COFs在不同场景下的应用潜力。
利用COFs的开放多孔结构和优异的稳定性,将金属纳米颗粒与COFs相结合制备金属纳米颗粒功能化COFs复合材料,该复合材料不仅具有金属纳米颗粒突出的催化活性,还具有COFs强大的稳定性,在样品前处理以及催化领域受到广泛关注。利用银纳米颗粒(AgNPs)与不饱和C=C双键之间的电荷转移相互作用以及COFs基质与不饱和C=C双键之间的π-π堆叠作用,有望实现复杂样品中不饱和分析物的选择性富集萃取,展示银纳米颗粒功能化COFs与众不同的样品前处理能力;同时银纳米颗粒功能化COFs具有金属银纳米颗粒的催化活性,可作为一种纳米酶用于比色检测。这种基于颜色变化直接检测分析物的技术,有望成为一种理想的快速检测技术。因此,银纳米颗粒功能化共价有机框架可实现在模拟酶催化、选择性富集检测等不同领域的应用,研究意义重大,应用前景广阔。
发明内容
本发明的目的在于提供银纳米颗粒功能化共价有机框架微球。该类微球既可作为选择性富集萃取吸附剂,又可作为用于比色检测的纳米酶。本发明采用合成后原位还原的方式在共价有机框架微球上负载银纳米颗粒实现银纳米颗粒功能化共价有机框架微球的制备。一方面,利用微球上的AgNPs与不饱和C=C双键之间电荷转移作用以及共价有机框架与不饱和C=C双键之间的π-π堆积作用,实现复杂样品中微量不饱和分析物的选择性富集与分析;另一方面,银纳米颗粒功能化共价有机框架微球还具有优异的类氧化酶活性,在氧气存在的条件下可氧化3,3',5,5'-四甲基联苯胺(TMB)为蓝色的oxTMB,而加入多巴胺后,生成的oxTMB量变少导致紫外分光光度计测得的吸光度降低,进而实现多巴胺的可视化快速检测。本发明展示了银纳米颗粒功能化共价有机框架微球的多重性能,进一步开拓了共价有机框架材料在不同领域的应用。
为实现上述目的,本发明采用如下技术方案:
银纳米颗粒功能化共价有机框架微球,其特征在于:所述的微球采用合成后原位还原的方式在基质共价有机框架微球上负载银纳米颗粒实现银纳米颗粒功能化共价有机框架微球的制备,所述的基质共价有机框架微球由室温下通过共价有机框架制备配体之间的席夫碱反应制备,所述的制备过程以基质共价有机框架微球作为载体捕获溶液中的银离子,接着利用原位还原反应将捕获在共价有机框架微球上的银离子还原生成银纳米颗粒,实现银纳米颗粒功能化共价有机框架微球的制备。
上述银纳米颗粒功能化共价有机框架微球的制备方法,包括以下步骤:
1)基质共价有机框架微球的制备:以1,3,5-三(4-氨苯基)苯为氨基配体,2,5-二乙烯基-1,4-苯二甲醛、对苯二甲醛或2,5-二甲氧基苯-1,4-二甲醛为醛基配体,其中氨基配体与醛基配体的摩尔比为2:3,以5 mL乙腈作为溶剂,超声分散溶解,加入0.3 mL至1.5mL 12 mol/L乙酸作为催化剂,室温下反应72小时,离心得到的沉淀物分别用四氢呋喃和乙醇洗涤3次,60℃真空干燥箱中干燥24小时,分别得到基质共价有机框架微球COF-V、COFTAPB-TPA和COFTAPB-DMTP。
2)三种还原方式制备银纳米颗粒功能化共价有机框架微球
S1:制备AgNPs@COF-V-SH微球:
(1)巯基功能化共价有机框架微球的制备:将上述合成的COF-V微球和2 mg偶氮二异丁腈置于烧瓶中,加入4 mL 1,2-乙二硫醇,室温搅拌48小时,得到均匀的黄褐色悬浊液,离心产物用丙酮洗涤3次,60℃真空干燥箱中干燥24小时,得到巯基功能化共价有机框架微球COF-V-SH。
(2)制备AgNPs@COF-V-SH微球:取上述巯基功能化共价有机框架微球分散于44.6mL二次水中,室温下,以4-7 mL/h的流速将10 mL硝酸银溶液缓慢加入到上述溶液中,搅拌24小时,离心沉淀物分别用二次水和乙醇各洗3次,60℃真空干燥箱中干燥24小时,得到AgNPs@COF-V-SH微球。
S2:制备AgNPs@COFTAPB-TPA微球:将100 mg上述制备的COFTAPB-TPA微球分散在20 mL乙醇中,超声1小时,取70 mg硝酸银溶于5 mL二甲基亚砜并加入到上述分散液中,再超声30分钟,之后将混合物置于油浴锅中加热24小时,最后用N,N-二甲基甲酰胺和乙醇分别洗涤以除去未反应的杂质,将所得粉末置于60℃真空干燥箱中干燥24小时,得到AgNPs@COFTAPB-TPA微球。
S3:制备AgNPs@COFTAPB-DMTP微球:取10 mg上述制备的COFTAPB-DMTP分散于5 mL乙醇中,超声1小时,之后加入30 mg聚乙烯吡咯烷酮,4.5 mL二次水以及0.5 mL硝酸银溶液,再超声1小时,待超声结束之后向上述溶液中加入0.5 mL柠檬酸钠溶液,搅拌10分钟,在剧烈搅拌下,缓慢向溶液中加入0.5 mL葡萄糖溶液,之后室温搅拌15小时,最后离心沉淀物用乙醇和水混合物洗涤3次,60℃真空干燥箱中干燥24小时,得到AgNPs@COFTAPB-DMTP微球。
银纳米颗粒功能化共价有机框架微球的多领域应用展示:
1)作为分散固相萃取吸附剂:以银纳米颗粒功能化共价有机框架微球(AgNPs@COF-V-SH)为选择性吸附剂,通过分散固相萃取,实现复杂样品中不饱和分析物的净化、萃取、富集,最后结合高效液相色谱***,实现富集的分析物的高效检测。具体步骤如下:
①分散固相萃取:以体积比为1:1的甲醇/水溶液制备的样品溶液,取1 mL该溶液于离心管中,加入0.5 mg AgNPs@COF-V-SH微球,超声分散均匀,放置于恒温混匀仪中,室温恒温分散固相萃取3分钟,之后离心移除上清液;
②解吸:向离心管中加入1 mL乙腈饱和正己烷,超声解吸5分钟,之后快速离心,收集解吸液,使用针头过滤器过滤;将解吸液用氮气吹干,再以0.2 mL流动相重溶,制备待测溶液;
③高效液相色谱***检测:将待测溶液直接进样至高效液相色谱(HPLC)***检测。
2)作为管内固相微萃取吸附剂:以银纳米颗粒功能化共价有机框架微球(AgNPs@COFTAPB-TPA)为管内固相微萃取吸附剂,构建银纳米粒子管内微萃取-银离子高效液相色谱在线联用***(on-line in-tube AgNPs-SPME-Ag+-HPLC),实现复杂样品中不饱和分析物的在线萃取与高效分析。具体步骤如下:
①制备AgNPs@COFTAPB-TPA填充固相微萃取柱:采用匀浆法将60 mg AgNPs@COFTAPB-TPA微球填充入不锈钢柱中,之后使用高压输液泵,以正己烷为流动相,以0.08 mL/min的流速冲洗填充得到的固相微萃取(SPME)柱 1小时,制得AgNPs@COFTAPB-TPA填充SPME柱。
②联用***构建:以AgNPs@COFTAPB-TPA填充SPME柱作为选择性吸附剂,采用“六通阀+十通阀”方式构建银纳米粒子管内微萃取-银离子高效液相色谱在线联用***。
③在线富集与洗脱:待SPME柱与色谱分析柱稳定后,通过进样器将待测样品注入0.5 mL定量环中;随后,通过上样相将定量环中的样品溶液带入AgNPs@COFTAPB-TPA填充SPME柱,将待测样品完全通入SPME柱中进行在线富集;之后,将上样相更换为洗脱相(正己烷/二氯甲烷=99.2%/0.8%,v/v),并通过泵A以0.1 mL/min的流速将SPME柱上萃取的分析物进行洗脱。
④在线检测:洗脱程序完成后,将十通阀调节至INJECT状态,此时流动相通过泵B以1.0 mL/min的流速将定量环中收集的洗脱液推入色谱分析柱中进行分析检测。
3) 作为纳米酶进行比色检测:以银纳米颗粒功能化共价有机框架微球(AgNPs@COFTAPB-DMTP)为模拟酶材料,结合紫外-分光光度计,通过颜色变化,实现复杂样品中分析物的比色检测。具体步骤如下:将300 μL的AgNPs@COFTAPB-DMTP分散液(最终浓度为40 μg/mL)和600 μL的TMB溶液(最终浓度为0.6 mM)加到1.5 mL的HAC-NaAC溶液(0.2 M,pH 4.0)中,混合均匀后在室温下反应5分钟,之后将不同浓度的多巴胺(DA)标准溶液(0-100 μM)分别加入到上述混合液中,混合均匀后在室温下反应,之后用紫外-可见吸收光谱仪测量反应溶液的吸收光谱,记录波长在657 nm处的吸光度值。
本发明的有益效果在于:相较于传统的复合材料,本发明提供的银纳米颗粒功能化共价有机框架微球不仅可以作为选择性吸附剂实现不饱和化合物的分散固相萃取和管内固相微萃取,还可以作为一种纳米酶实现复杂生物体液样品中微量目标物的高效比色检测。
附图说明
图1为本发明制备的银纳米颗粒功能化共价有机框架微球(AgNPs@COF-V-SH)的透射电镜(TEM)图(图1a)和XPS表征图(图1b)。
图2为本发明制备的银纳米颗粒功能化共价有机框架微球(AgNPs@COFTAPB-TPA)的透射电镜(TEM)图(图2a)和XPS表征图(图2b)。
图3为本发明制备的银纳米颗粒功能化共价有机框架微球(AgNPs@COFTAPB-DMTP)的透射电镜(TEM)图(图3a)和XPS表征图(图3b)。
图4是高效液相色谱图。a是0.5 μg/mL的二十碳四烯酸甲酯(ARAME)和二十二碳六烯酸甲酯(DHAME)加标奶粉直接检测的色谱图;b是空白奶粉经以本发明制备的银纳米颗粒功能化共价有机框架(AgNPs@COF-V-SH)作为分散固相萃取吸附剂分散固相萃取后HPLC检测的色谱图;c是0.5 μg/mL的ARAME和DHAME加标奶粉经AgNPs@COF-V-SH微球分散固相萃取后HPLC检测的色谱图;d是5.0 μg/mL的ARAME和DHAME标准品的色谱图。峰归属:(1) DHAME;(2) ARAME。
图5是高效液相色谱图。a是in-tube Ag NPs-SPME-Ag+-HPLC分析加标奶茶样品;b是in-tube Ag NPs-SPME-Ag+-HPLC分析空白奶茶样品;c是常规银离子液相色谱(Ag+-HPLC)分析加标奶茶样品。峰归属:(1) 9t-C18:1; (2) 9t,12t-C18:2; (3) 9c-C18:1;(4) 9c,12c-C18:2。
图6是以本发明制备的银纳米颗粒功能化共价有机框架(AgNPs@COFTAPB-DMTP)作为纳米酶对不同浓度的多巴胺溶液进行比色检测的照片和吸收光谱。
图7是以本发明制备的银纳米颗粒功能化共价有机框架(AgNPs@COFTAPB-DMTP)作为纳米酶对不同浓度的多巴胺溶液进行比色检测的线性校准曲线图。
具体实施方式
为了使本发明所述内容更加便于理解,下面结合具体实施例对本发明所述的技术方案进行清楚、完整地描述,显然,所描述的实施例是本发明一部分实施例,而不是全部的实施例。
实施例1
银纳米颗粒功能化共价有机框架微球及其富集萃取应用,包括以下步骤:
(1)制备基质共价有机框架:将物质的量比为2:3的1,3,5-三(4-氨苯基)苯和2,5-二乙烯基-1,4-苯二甲醛添加到5 mL的乙腈中,超声分散溶解,加入0.35 mL 12 mol/L乙酸作为催化剂,室温下反应72小时,离心得到的沉淀物分别用四氢呋喃和乙醇洗涤3次,60℃真空干燥箱中干燥24小时,得到基质共价有机框架微球COF-V。
(2)制备巯基功能化共价有机框架:将20 mg上述合成的COF-V微球和2 mg偶氮二异丁腈置于烧瓶中,加入4 mL 1,2-乙二硫醇,室温搅拌48小时,得到均匀的黄褐色悬浊液,离心产物用丙酮洗涤3次,60℃真空干燥箱中干燥24小时,得到巯基功能化共价有机框架微球COF-V-SH。
(3)制备AgNPs@COF-V-SH:取223 mg上述巯基功能化共价有机框架微球分散于44.6 mL二次水中,室温下,以6 mL/h的流速将10 mL硝酸银溶液缓慢加入到上述溶液中,搅拌24小时,离心沉淀物分别用二次水和乙醇各洗3次,60℃真空干燥箱中干燥24小时,得到最终产物AgNPs@COF-V-SH微球。
(4)富集检测:以体积比为1:1的甲醇/水溶液配制的待测样品溶液,取1 mL该溶液于离心管中,加入0.5 mg AgNPs@COF-V-SH微球,超声分散均匀,放置于恒温混匀仪中,室温恒温分散固相萃取3分钟,之后离心移除上清液;向离心管中加入1 mL乙腈饱和正己烷,超声解吸5分钟,之后快速离心,收集解吸液,使用针头过滤器过滤;将解吸液用氮气吹干,再以0.2 mL流动相重溶,制备待测溶液;将待测溶液直接进样至高效液相色谱(HPLC)***检测,检测使用的流动相为乙腈,流动相流速为1.0 mL/min,检测波长为221 nm,柱温为40℃。
按照实施例1制备的银纳米颗粒功能化共价有机框架微球(AgNPs@COF-V-SH),对其进行透射电镜(TEM)和X射线光电子能谱(XPS)表征。从透射电镜图1a中可以发现大量电子束无法穿透的黑色小点,皆为AgNPs颗粒,均匀地分布在AgNPs@COF-V-SH微球表面上。如图1b所示,该材料的全波段XPS能谱图中可明显看到C、N、O、S、Ag这五种元素信号,证明AgNPs成功负载在COF-V-SH微球上。
按照实施例1制备的银纳米颗粒功能化共价有机框架微球(AgNPs@COF-V-SH)作为分散固相萃取吸附剂,结合高效液相色谱***(HPLC),分析奶粉样品中的多不饱和脂肪酸甲酯。如图4所示,HPLC直接检测不饱和脂肪酸甲酯标准混合物时,对应的检测峰归属于二十二碳六烯酸甲酯(DHAME)和二十碳四烯酸甲酯(ARAME)(曲线d)。而当直接使用HPLC***检测样品时,奶粉基质干扰严重,峰展宽大,分析对象无法分离识别(曲线a)。而使用银纳米颗粒功能化共价有机框架(AgNPs@COF-V-SH)作为分散固相萃取吸附剂,奶粉样品中的基质干扰明显减弱,在检测对象的色谱峰附近没有干扰物存在(曲线b)。使用该方法对加标ARAME和DHAME(浓度0.5 μg/mL)的奶粉样品进行分散固相萃取后(曲线c),可以看到清晰识别ARAME和DHAME的色谱峰,充分说明了以AgNPs@COF-V-SH微球为吸附剂的分散固相萃取方法,可实现奶粉样品中微量ARAME和DHAME的高效富集萃取。
实施例2
银纳米颗粒功能化共价有机框架微球及其富集萃取应用,包括以下步骤:
(1)制备基质共价有机框架:将物质的量比为2:3的1,3,5-三(4-氨苯基)苯和对苯二甲醛添加到5 mL的乙腈中,超声分散溶解,加入1.0 mL 12 mol/L乙酸作为催化剂,室温下反应72小时,离心得到的沉淀物分别用四氢呋喃和乙醇洗涤3次,60℃真空干燥箱中干燥24小时,得到基质共价有机框架微球COFTAPB-TPA。
(2)制备AgNPs@COFTAPB-TPA:将100 mg上述制备的COFTAPB-TPA微球分散在20 mL乙醇中,超声1小时,取70 mg硝酸银溶于5 mL二甲基亚砜并加入到上述分散液中,再超声30分钟,之后将混合物置于80℃油浴锅中加热24小时,最后用N,N-二甲基甲酰胺和乙醇分别洗涤以除去未反应的杂质,将所得粉末置于60℃真空干燥箱中干燥24小时,得到AgNPs@COFTAPB-TPA微球。
(3)制备AgNPs@COFTAPB-TPA填充SPME:采用匀浆法将60 mg的AgNPs@COFTAPB-TPA微球填充入不锈钢柱中,之后使用高压输液泵,以正己烷为流动相,以0.08 mL/min的流速对填充得到的SPME柱冲洗1小时,获得AgNPs@COFTAPB-TPA填充固相微萃取柱。
(4)联用***构建:以AgNPs@COFTAPB-TPA填充SPME柱作为选择性吸附剂,采用“六通阀+十通阀”方式构建银纳米粒子管内微萃取-银离子高效液相色谱在线联用***。
(5)在线检测:在SPME柱与色谱分析柱稳定后,通过进样器将待测样品注入0.5 mL定量环中;随后,通过上样相将定量环中的样品溶液带入AgNPs@COFTAPB-TPA填充SPME柱,将待测样品完全通入SPME柱中进行在线富集;之后,将上样相更换为洗脱相(正己烷/二氯甲烷=99.2%/0.8%,v/v),并通过泵A以0.1 mL/min的流速将SPME柱上萃取的样品进行洗脱;洗脱程序完成后,将十通阀调节至INJECT状态,此时流动相通过泵B以1.0 mL/min的流速将定量环中收集的洗脱液推入色谱分析柱中进行分析检测。
按照实施例2制备的银纳米颗粒功能化共价有机框架微球(AgNPs@COFTAPB-TPA),对其进行透射电镜(TEM)和X射线光电子能谱(XPS)表征。从透射电镜图2a中可以看到AgNPs@COFTAPB-TPA微球呈均匀的球形结构且表面均匀分布着许多不透光的小颗粒,即为AgNPs。如图2b所示,AgNPs@COFTAPB-TPA微球的全波段能谱图表明制备的AgNPs@COFTAPB-TPA微球主要由C、N、O、Ag元素组成,这一结果进一步证实了AgNPs成功还原到了COFTAPB-TPA微球上。
以实施例2制备的银纳米颗粒功能化共价有机框架微球(AgNPs@COFTAPB-TPA)作为管内固相萃取吸附剂,构建in-tube AgNPs-SPME-Ag+-HPLC在线联用***,分析奶茶样品种顺反式单双不饱和脂肪酸甲酯。如图5所示,在对加标奶茶样品使用常规Ag+-HPLC***的直接进样分析模式时(曲线c),奶茶样品中的基质对分析对象造成极强的干扰,与分析对象的吸收色谱峰产生了重叠。而当使用构建的in-tube AgNPs-SPME-Ag+-HPLC在线联用***进行分析时(曲线a),样品基质的干扰信号明显下降,减小了对分析对象识别检测的影响,分析对象的信号峰清晰可见,由此可以证明AgNPs@COFTAPB-TPA微球不仅具有良好的富集能力,而且具有令人满意的除杂能力。通过in-tube AgNPs-SPME-Ag+-HPLC***对空白奶茶实际样品的分析(曲线b),可以发现实际奶茶样品中存在极少量的顺式不饱和脂肪酸甲酯。
实施例3
银纳米颗粒功能化共价有机框架微球及其比色检测应用,包括以下步骤:
(1)制备基质共价有机框架:将物质的量比为2:3的1,3,5-三(4-氨苯基)苯和2,5-二甲氧基苯-1,4-二甲醛添加到5 mL的乙腈中,超声分散溶解,加入1.5 mL 12 mol/L乙酸作为催化剂,室温下反应72小时,离心得到的沉淀物分别用四氢呋喃和乙醇洗涤3次,60℃真空干燥箱中干燥24小时,得到基质共价有机框架微球COFTAPB-DMTP。
(2)制备AgNPs@COFTAPB-DMTP:取10 mg上述制备的COFTAPB-DMTP加入到5 mL乙醇中,超声1小时,之后加入30 mg聚乙烯吡咯烷酮,4.5 mL二次水以及0.5 mL硝酸银溶液,接着超声1小时,向上述溶液中加入0.5 mL柠檬酸钠溶液于磁力搅拌器上搅拌10分钟,在剧烈搅拌下,缓慢向溶液中加入0.5 mL葡萄糖溶液,之后室温搅拌15小时,最后离心沉淀物用乙醇和水混合物洗涤3次,60℃真空干燥箱中干燥24小时,得到AgNPs@COFTAPB-DMTP微球。
(3)比色检测:将300 μL的AgNPs@COFTAPB-DMTP分散液(最终浓度为40 μg/mL)和600μL的TMB溶液(最终浓度为0.6 mM)加到1.5 mL的HAC-NaAC溶液(0.2 M,pH 4.0)中,混合均匀后在室温下反应5分钟,之后将不同浓度的多巴胺标准溶液(0-100 μM)分别加入到上述混合液中,混合均匀后在室温下反应,之后用紫外-可见吸收光谱仪测量反应溶液的吸收光谱,记录波长在657 nm处的吸光度值。
按照实施例3制备的银纳米颗粒功能化共价有机框架微球(AgNPs@COFTAPB-DMTP),对其进行透射电镜(TEM)和X射线光电子能谱(XPS)表征。从透射电镜图3a可以直观地看到AgNPs@COFTAPB-DMTP呈均匀的花状球形且由许多不透光的小颗粒分布在表面,说明AgNPs成功地在COFTAPB-TPA微球表面还原。如图3b所示,AgNPs@COFTAPB-DMTP微球的XPS图中主要可以看到C、N、O、Ag四种元素信号,再一次证明AgNPs成功负载在基质共价有机框架上。
按照实施例3制备的银纳米颗粒功能化共价有机框架微球(AgNPs@COFTAPB-DMTP)作为纳米酶,构建以AgNPs@COFTAPB-DMTP微球作为探针、紫外-可见分光光度计作为读出装置的简单且快速的比色法,实现对实际样中多巴胺的定量检测。银纳米颗粒功能化共价有机框架微球具有较强的类氧化酶活性和对底物3,3',5,5'-四甲基联苯胺(TMB)的高亲和性,其介导的类氧化酶反应产生的oxTMB量在加入多巴胺后显著减少。图6是对不同浓度的多巴胺溶液进行比色检测的照片和吸收光谱。可以发现随着多巴胺浓度的上升,溶液的颜色逐渐变浅,而且从其对应的紫外-可见吸收光谱中可以看出657纳米处的吸光度逐渐降低。图7是不同浓度多巴胺的紫外-可见吸光度线性关系图,该线性方程分别是1-25 μM对应的Δ657 nm=0.01004 CDA+0.04410(R2=0.999)和25-150 μM对应的Δ657 nm=0.00362 CDA+0.19928(R2=0.983)。以上结果显示了本发明提供的银纳米颗粒功能化共价有机框架微球可作为纳米酶在比色检测领域具有良好的应用前景。
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (5)
1.一种银纳米颗粒功能化共价有机框架微球的制备方法,其特征在于:包括以下步骤:
1)基质共价有机框架微球的制备:以1,3,5-三(4-氨苯基)苯为氨基配体,2,5-二乙烯基-1,4-苯二甲醛、对苯二甲醛或2,5-二甲氧基苯-1,4-二甲醛为醛基配体,其中氨基配体与醛基配体的摩尔比为2:3,以乙腈为溶剂,超声分散溶解,再加入12 mol/L乙酸作为催化剂,室温下反应72小时;离心,沉淀物用四氢呋喃和乙醇各洗3次,60℃真空干燥24小时,得到基质共价有机框架微球COF-V、COFTAPB-TPA或COFTAPB-DMTP;
2)原位还原制备银纳米颗粒功能化共价有机框架微球
S1:制备AgNPs@COF-V-SH微球:将20 mgCOF-V、2 mg偶氮二异丁腈和4 mL1,2-乙二硫醇混合,室温搅拌48小时,离心,产物用丙酮洗涤3次,60℃真空干燥24小时,得到巯基功能化共价有机框架微球COF-V-SH;将COF-V-SH分散于44.6 mL二次水中,室温下,以4-7 mL/h的流速缓慢加入10 mL硝酸银溶液,搅拌24小时,离心,沉淀物用二次水和乙醇各洗3次,60℃真空干燥24小时,得到AgNPs@COF-V-SH微球;
S2:制备AgNPs@COFTAPB-TPA微球:将100 mg COFTAPB-TPA分散在20 mL乙醇中,超声1小时,将70 mg硝酸银溶于5 mL二甲基亚砜中并加入到分散液中,再超声30分钟,油浴加热反应24小时,用N,N-二甲基甲酰胺和乙醇洗涤,60℃真空干燥24小时,得到AgNPs@COFTAPB-TPA微球;
S3:制备AgNPs@COFTAPB-DMTP微球:将10 mg COFTAPB-DMTP分散于5 mL乙醇中,超声1小时,加入30 mg聚乙烯吡咯烷酮、4.5 mL二次水和0.5 mL硝酸银溶液,再超声1小时,加入0.5 mL柠檬酸钠溶液,搅拌10分钟,在剧烈搅拌下,缓慢加入0.5 mL葡萄糖溶液,室温搅拌15小时,离心,沉淀物用乙醇溶液洗涤3次,60℃真空干燥24小时,得到AgNPs@COFTAPB-DMTP微球。
2.一种如权利要求1所述的方法制得的银纳米颗粒功能化共价有机框架微球。
3.一种如权利要求1所述的方法制得的银纳米颗粒功能化共价有机框架微球的应用,其特征在于:银纳米颗粒功能化共价有机框架微球AgNPs@COF-V-SH作为分散固相萃取吸附剂,实现复杂样品中微量不饱和分析物的选择性富集与高效分析。
4.一种如权利要求1所述的方法制得的银纳米颗粒功能化共价有机框架微球的应用,其特征在于:银纳米颗粒功能化共价有机框架微球AgNPs@COFTAPB-TPA作为在线管内固相微萃取吸附剂,实现复杂样品中微量不饱和分析物的选择性富集与高效检测。
5.一种如权利要求1所述的方法制得的银纳米颗粒功能化共价有机框架微球的应用,其特征在于:银纳米颗粒功能化共价有机框架微球AgNPs@COFTAPB-DMTP作为具有类氧化酶活性的纳米酶,实现生物体液中微量多巴胺的比色检测。
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