CN109134886A - 一种h2s刺激响应水凝胶的制备及应用 - Google Patents
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Abstract
本发明公开了一种H2S刺激响应水凝胶的制备及应用,所述方法是采用壳聚糖的分子链上含有大量氨基和羟基,能与Cu2+形成配位结构,触发壳聚糖形成稳定的水凝胶,且成胶迅速,约五秒内即可形成水凝胶。当环境中存在H2S时,能将水凝胶中的交联剂Cu2+竞争出来,导致水凝胶瓦解,释放水凝胶中包埋的探针,实现对H2S定量检测或药物可控释放;本发明方案操作简单、成本低、合成速度快且实施便利,其所制得的H2S刺激响应水凝胶性能稳定且不仅可用于H2S检测,还可用于在H2S刺激下进行药物的可控释放,另外在样品检测、食品安全分析、工业环境监测、药物释放材料等具有广阔应用前景。
Description
技术领域
本发明方案涉及分析化学领域,具体涉及一种H2S刺激响应水凝胶的制备及应用,其可用于样品中H2S的检测和H2S触发的药物的释放。
背景技术
水凝胶是一类能够在水中溶胀并且具有高含水量的高分子聚合物材料。该材料通过高分子链之间的作用力(如分子间静电作用、氢键等作用力)或化学键形成三维网状结构。研究表明一些水凝胶能感知外界环境刺激,如pH值、温度、离子强度、压力、光、电、待测目标物等微小变化,导致水凝胶结构、能量状态等发生变化并产生一定的信号响应。基于高分子水凝胶对外界环境的敏感性,研究者们设计了许多功能化刺激响应型高分子水凝胶材料,构建了目标物刺激响应的传感器,实现了金属离子、生物大分子和细胞等物质分析检测。
壳聚糖由甲壳素经过脱乙酰化处理后获得,是自然界中含量最丰富的天然碱性多糖。壳聚糖的分子链上含有大量氨基和羟基,能与许多小分子、离子或者聚合物反应生成壳聚糖基的衍生物或者高分子复合材料。壳聚糖可以与其他亲水性单体通过物理或化学交联的形式形成具有网格结构的高分子聚合物材料,其中壳聚糖水凝胶是最常见的壳聚糖基高分子材料。
发明内容
本发明的目的在于提供一种H2S刺激响应水凝胶的制备及应用,其可用于环境样品、生物样品等场景中H2S的高灵敏检测以及在H2S触发的药物释放。
为了实现上述的技术目的,本发明采用的技术方案为:
一种H2S刺激响应水凝胶的制备方法,其包括如下步骤:
(1)按照1 g:200 mL的固液比将壳聚糖溶解于醋酸溶液中,然后对其进行超声处理以去除溶液中悬浮的气泡,制得溶液A;
(2)往溶液A中加入化学探针,然后将其分散均匀在溶液A中,制得溶液B;
(3)往溶液B中加入铜离子并混合均匀,使其触发壳聚糖单体聚合,制得水凝胶;
(4)将制得的水凝胶进行洗涤处理后,去除未聚合的铜离子以及多余的化学探针,即可制得H2S刺激响应水凝胶。
进一步,步骤(1)中醋酸溶液的质量百分浓度为0.2%。
优选的,步骤(1)中壳聚糖的添加量为0.025 g,醋酸溶液的添加量为5 mL。
优选的,步骤(2)中的化学探针为1 mM的亚甲基蓝,其添加量为20 μL。
进一步,步骤(4)中的洗涤处理的洗涤液为蒸馏水。
优选的,步骤(4)中洗涤处理的次数为3次。
进一步,步骤(4)中还包括对洗涤处理后的水凝胶用滤纸吸干游离的水分。
根据上述制备方法制得的H2S刺激响应水凝胶的应用之一,将制得的H2S刺激响应水凝胶用于H2S的检测,具体为:将含有H2S的待检测物加入到H2S刺激响应水凝胶中进行混合,将H2S刺激响应水凝胶中的Cu2+竞争置换出,导致水凝胶瓦解,令水凝胶中包埋的化学探针被释放,通过检测释放出的化学探针浓度来间接定量检测到待检测物的H2S含量。
根据上述制备方法制得的H2S刺激响应水凝胶的应用之一,将制得的H2S刺激响应水凝胶中包埋药物,然后将其与含H2S的物质混合后,实现包埋药物的释放。
根据上述制备方法制得的H2S刺激响应水凝胶的应用之一,将制得的H2S刺激响应水凝胶作为物体外表面包覆物,然后将其与含H2S的物质混合后,实现所包覆物体的释放。
采用上述的技术方案,本发明具有的有益效果为:本发明方案操作简单、成本低、合成速度快且实施便利,其所制得的H2S刺激响应水凝胶性能稳定且不仅可用于H2S检测,还可用于在H2S刺激下进行药物的可控释放,另外在样品检测、食品安全分析、工业环境监测、药物释放材料等具有广阔应用前景。
附图说明
下面结合附图和具体实施方式对本发明做进一步的阐述:
图1为本发明方案的简要制备方法原理示意图;
图2为本发明方案制得的H2S刺激响应水凝胶的刺激响应标准曲线,其中,图2(A)由下至上a-j依序表示浓度为1,5,10,15,25,40,60 μM的Na2S。
具体实施方式
一种H2S刺激响应水凝胶的制备方法,其包括如下步骤:
(1)按照1 g:200 mL的固液比将壳聚糖溶解于醋酸溶液中,然后对其进行超声处理以去除溶液中悬浮的气泡,制得溶液A;
(2)往溶液A中加入化学探针,然后将其分散均匀在溶液A中,制得溶液B;
(3)往溶液B中加入铜离子并混合均匀,使其快速触发壳聚糖单体聚合,制得水凝胶;
(4)将制得的水凝胶进行洗涤处理后,去除未聚合的铜离子以及多余的化学探针,即可制得H2S刺激响应水凝胶。
本方案所采用壳聚糖的分子链上含有大量氨基和羟基,能与Cu2+形成配位结构,触发壳聚糖形成稳定的水凝胶,且成胶迅速,约五秒内即可形成水凝胶。
当环境中存在H2S时,能将水凝胶中的交联剂Cu2+竞争出来,导致水凝胶瓦解,释放水凝胶中包埋的探针,实现对H2S定量检测或药物可控释放。
实施例1
如图1所示,一种H2S刺激响应水凝胶的制备方法,其包括如下步骤:
(1)将0.025 g壳聚糖溶解于5 mL 质量浓度为0.2%的醋酸溶液中,然后通过漩涡混匀器将壳聚糖完全溶解后,再对其进行超声处理以去除溶液中悬浮的气泡,制得溶液A;
(2)往溶液A中加入20 μL 1 mM的亚甲基蓝溶液,然后将其分散均匀在溶液A中,制得溶液B;
(3)取300 μL壳聚糖与亚甲基蓝混合液于2 mL离心管中,加入Cu2+作为水凝胶的触发剂,并在漩涡混匀器上迅速混匀,使壳聚糖水溶液能在5 s内迅速聚合,形成水凝胶(Cu-CS)。;
(4)将制得的水凝胶用蒸馏水进行洗涤处理后,去除未聚合的铜离子以及多余的亚甲基蓝,然后滤纸对其表面进行水分吸干,即可制得H2S刺激响应水凝胶。
测试
采用Na2S作为H2S的供体,并通过逐级稀释的方式得到不同浓度的Na2S标准品,然后将上述标准品在使用前现配现用。
将Na2S标准品加入到实施例中制得的H2S刺激响应水凝胶(即Cu-CS)水凝胶),通过漩涡混匀器将二者充分混匀,放置在室温中孵育。此时,Na2S与Cu-CS水凝胶产生竞争反应,即水凝胶中的Cu2+与S2-发生反应,生成CuS,导致Cu-CS水凝胶结构瓦解,释放亚甲基蓝。孵育完成后,使用移液枪将上清液移取出来,并通过离心分离CuS,保留含有亚甲基蓝的上清液待测。
本方法通过测定亚甲基蓝的浓度进而对样品中的H2S进行定量检测。亚甲基蓝定量检测采用差分脉冲伏安法(DPV)进行。
首先,玻碳电极(GCE,3 mm)在麂皮上依次使用1.0、0.3、0.05 μm的Al2O3粉末进行抛光打磨,并依次使用乙醇、食人鱼洗液和蒸馏水超声清洗。
接着,将上述处理后的电极浸泡在0.5 M的H2SO4溶液中,以Ag/AgCl作为参比电极,以铂丝作为对电极,采用循环伏安法在-0.2 ~ 1.0 V电位范围内进行扫描,直至得到稳定的循环伏安图。将GCE用蒸馏水冲洗干净备用。
最后,将GCE置于上述含有亚甲基蓝的待测液中,采用DPV法对其进行定量检测。检测条件为:脉冲幅度:0.05 V;脉冲宽度:0.05 s;电位范围:-0.05 ~ 0.35 V。
以上所述仅为本发明的较佳实施例,凡依照本发明申请专利范围所做的均等变化与修饰,皆属于本发明的涵盖范围。
Claims (10)
1.一种H2S刺激响应水凝胶的制备方法,其特征在于:其包括如下步骤:
(1)按照1 g:200 mL的固液比将壳聚糖溶解于醋酸溶液中,然后对其进行超声处理以去除溶液中悬浮的气泡,制得溶液A;
(2)往溶液A中加入化学探针,然后将其分散均匀在溶液A中,制得溶液B;
(3)往溶液B中加入铜离子并混合均匀,制得水凝胶;
(4)将制得的水凝胶进行洗涤处理后,即可制得H2S刺激响应水凝胶。
2.根据权利要求1所述的H2S刺激响应水凝胶的制备方法,其特征在于:步骤(1)中醋酸溶液的质量百分浓度为0.2%。
3. 根据权利要求2所述的H2S刺激响应水凝胶的制备方法,其特征在于:步骤(1)中壳聚糖的添加量为0.025 g,醋酸溶液的添加量为5 mL。
4. 根据权利要求3所述的H2S刺激响应水凝胶的制备方法,其特征在于:步骤(2)中的化学探针为1 mM的亚甲基蓝,其添加量为20 μL。
5.根据权利要求1所述的H2S刺激响应水凝胶的制备方法,其特征在于:步骤(4)中的洗涤处理的洗涤液为蒸馏水。
6.根据权利要求5所述的H2S刺激响应水凝胶的制备方法,其特征在于:步骤(4)中洗涤处理的次数为3次。
7.根据权利要求1所述的H2S刺激响应水凝胶的制备方法,其特征在于:步骤(4)中还包括对洗涤处理后的水凝胶用滤纸吸干游离的水分。
8.根据权利要求1至7之一所述制备方法制得的H2S刺激响应水凝胶的应用,其特征在于:将制得的H2S刺激响应水凝胶用于H2S的检测,具体为:将含有H2S的待检测物加入到H2S刺激响应水凝胶中进行混合,将H2S刺激响应水凝胶中的Cu2+竞争置换出,导致水凝胶瓦解,令水凝胶中包埋的化学探针被释放,通过检测释放出的化学探针浓度来间接定量检测到待检测物的H2S含量。
9.根据权利要求1至7之一所述的制备方法制得水凝胶的应用,其特征在于:在H2S刺激响应水凝胶中包埋药物,然后将其与含H2S的物质混合后,实现包埋药物的释放。
10.根据权利要求1至7之一所述的制备方法制得水凝胶的应用,其特征在于:将制得的H2S刺激响应水凝胶作为物体外表面包覆物,然后将其与含H2S的物质混合后,实现所包覆物体的释放。
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